Chemical And Polymer Industry Module - Toxics Use ...infohouse.p2ric.org/ref/32/31804.pdf ·...

- INSTITUTE

Udvmity of Marrrachuseos at Lowell One Uaiveraity Avenue Lowell, UA 01854 ~

Telephone: (508) 934-3275 FAX: (50s) 453-2332

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ACKNO WLEDGEMENTS

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I want to take this opportunity to thank the Toxic Use Reduction Institute

and Novacor Chemicals Inc. for their support in preparing this

curriculum.

Also, I want to recognize Tom Scurfield, Peter Cowley, Process

Technology Engineering with Novacor Chemicals Inc., Brooke Clibbon

and Sarah Angers for their administrative support within the Nova

Organization.

TOXIC USE REDUCTION PLANNING

1N THE CHEMICAL AND POLYMER INDUSTRIES

TABLE OF CONTENTS . ~-~ _ ~ ~ -

INTRODUCTION ................................................. 2 . 1.0 INDUSTRY OVERVIEW ............................... 4 . 2.0 PROCESS CHARACTERIZATION .................. 10

3.0 TOXIC USE REDUCTION OPTIONS ............... 24

4.0 TUR PLANNING PROCESS CHECKLIST ......... 29

REFERENCES ..................................................... 36

SUPPLEMENTAL READINGS ................................. 37

CHEMICAL AND POLYMER INDUSTRY MODULE

INTRODUCTION

In this specialized module of the Chemical and Polymer Industry, we willoverview

processes of specific industry areas, develop an understanding for process

characterization and toxic use reduction options within these areas.

The public feels threatened by the chemical industry. Survey after survey by the

Chemical Manufacturers Association (CMA) shows that people rank the industry as

one of the nations leading environmental and public health risks. Chemical companies

at first responded to these feelings by attributing them simply to a failure to

communicate the positive side of the industry and its good environmental and safety

record. But this complacency was abruptly ended by well publicized incidents such as

Bhopal, Love Canal and others, all strung together by widely reported discharges into

the air, the waterways and the ground. Industry leaders realized they had a poor

image because they really did have performance problems. In 1988 CMA's Board of

Directors adopted an initiative called "Responsible Care: A Public Commitment".

Grounded in existing proactive programs, responsible care calls for continuous

improvement by the Chemical Industry in Health, Safety and Environmental Quality.

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Responsible Care is an ongoing process, and a call for action to achieve these

primary goals:

Improved chemical processes

b Enhanced practices and procedures

b

F Reliable communication and dialogue

Reduction of every kind of waste, accident, incident and emission

b Heightened public scrutiny and input

The Responsible Care Pollution Prevention Code is designed to improve the industry's

ability to protect people and the environment by generating less waste and minimizing

emissions. The Pollution Prevention Code seeks voluntary, ongoing, long term

reductions in all pollutants released to the environment '.

With the Toxic Use Reduction Act legislation, the Chemical Industry has an additional

tool to assist in meeting the goals of responsible care in minimizing risk to customers,

employees, the public and the environment.

Toxic Use Reduction planning for the Chemical and Polymer Industries provides a

systematic approach to identifying and implementing reduction options to minimize the ~

potential for environmental losses.

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by Larry R. Morris Novacor Chemicals Inc.

ACKNOWLEDGEMENTS ~

I want to take this opportunity to thank the Toxic Use Reduction Institute

and Novacor Chemicals Inc. for their support in preparing this

curriculum.

Also, I want to recognize Tom Scurfield, Peter Cowley, Process

Technology Engineering with Novacor Chemicals Inc., Brooke Clibbon

and Sarah Angers for their administrative support within the Nova

Organization.


Under C w ’ s Responsible Care: Pollution Prevention Code of Practice, objectives for

compliance can be met with Toxic Use Reduction Planning.

As a total committment under Responsible Care, legislated standards become the

minimum standard to the development of a program. This program will:

b Protect our environment

b Provide reliable communication and dialogue to our public,

b Create a basis for ongoing, long term industry program growth.

1.0 INDUSTRY OVERVIEW

OaTECTIVEs: At the end of this section, participants d b e able to:

0 Develop a comprehensive understanding of specific

industry areas.

0 Understand the incentives of toxic use reduction options.

A wide variety of chemical related products and processes exist in Massachusetts

today. Process types can include polymerization, mixing, coating, compounding,

extraction, hydrogenation, extrusion molding and distillation operations, to name a few.

A wide variety of chemicals are used in these processes to produce feedstock,

intermediate, and finished products. In order to fullyunderstand how processes and

chemical origins relate, let’s look at the fractional distillation of petroleum and the

resultant products.

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. . . . - . . .* . . . _ . .-. . . . . . .

. tower,?:

. . , I ..' ,

. . 1 ,' ' " . . ,

Figure 9.6 Fractional distillation of petroleum. The molecules found in petroleum (crude oil) are separated on the basis of their boiling points. The petroleum is heated and the molecules with short carbon chains are drawn off. As the heat is increased, molecules with longer and longer carbon chains are drawn off. The molecules that remain are called heavy bottoms; they have very long carbon chains and are used to make asphalt and coke.

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These resultant products provide feedstocks for many other processes.

U t 7 s now look at material flows and processing of the hydrocarbons in the upper

range of the fractionating process.

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A guide to chemicals from hydrocarbons-some examples

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See Refining Handbook, HP, Kov. 1990

I

See Gas Handbook HP, Apr. 1990

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See Gas Handbook HP, Apr. 1990

L U a s v:

W

1

Ethylene 1 1 I I I I I f Propylene

I A l l l l i r r

Isoamylene

Isoprene

Hexenes - 87- 77 - - I -

Octenes -

Methyl chloride

Ethano 1 c

Protein - - Amines, Cl-C.12

L

. .

Nitric acid d

A”nium nitrate . . -

Ani 1 ine

Sulfonation

Polyesters

Dioctyl phthalate - . _

128 Hydrocarbon Processing, March 1991 -7-

. COLOR BLOCKS: processes in this issue. MMBERS:.year and page for processes in previous November HP issuc

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. . . . . . , _ . . . . .. . .. . - .

Po 1 ye thy l e

Ethanol Ethylmercapti 4 89-1011 Alcohols, all U

Acetic acid

Vinyl aceti __

Polyvinyl alcol

Oxalic ac

Chloroethy 1

EP mbl

Ethyl acryl

Polypropyl

Glycer

Propylene ox - I Butvraldehvde

I - . Butanol,

Buter

Acrylonitrile Adiponiti 4 85-118

Methyl ethyl ket

Butzmol, I___

Po lybute

Neo ac-

ABS re: Pol ybutad iene

-a- Hydrocarbon Processing, March 1991


It is interesting to note the wide variety of chemical products that result from

hydrocarbon processing.

ACTIVITY 1 Identifying Process and Chemical Uses

OBJECTIVE : To become familiar with chemical products and processes in a

downstream flow from chemical origins.

TASK: List the products and uses from the production of aromatics that

include benzene, toluene, and xylenes. List final consumer

product where applicable.

Think about challenges and incentives for these specific industries.

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2.0 PROCESS CHARACTERIZATION

OBJECTIVES : At the end of this section, participants willbe able to:

0 Develop an understanding of specific production processes,

production units, units of product, byproducts and

emissions,

Distinguish between specific industry products, processes,

production units, byproducts and emissions.

The following processes identify the production of acetone, alkyl benzene, aromatics,

benzene, cumene, cyclohexane, dimethyl formalide methanol, ethyl benzene, maleic

an hydride, polyethylene, polystyrene , polyvinyl chloride, polypropylene,

polycaproamide, styrene, and sulfonation . 3

These process flow diagrams are presented for future reference as well as providing

an understanding of chemical processes.

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Petrochemical Handbook ’91

Acetone Appllcatlonr A P’DCCSS for the efficient production of acetone and co-product phenol via the oxidation of cumene. Alphamethylstyme (AMS) and acetophemone (AP) may also be recovered as byproducts.

This process, pioncered by BP Chemicals, Hercules and Kel- logg in the original plant. has been continudly improved through extensive development and accumulated experience from the design and operation of more than 25 planu throughout the world. Process doscrlption: Cumene is oxidized (1) and (2) under mild conditions with air to produce cumene hydroperoxide which is concentrated and cleaved to phenol and acetone in the presence of an acid catalyst (3). Cleavage operation has been optimized to provide safety and high selectivity. The catalyst is removed and the mixture is fractionated to produce very high punty phenol (6). (7) and (8) and acetone products (4) v d (5).

The process produces extremely high quality acetone and ’phenol, suitable for the most demanding applications. Cumene consumption is less than 1.33 kg per kg of phenol. The fractionation train can be designed to separate AMS as a byproduct or hy- drogenate it to cumene and recycle to oxidation. AP may also be separated as a byproduct.

Particular attention has been paid to heat integration, environmental controls and safety systems. Steam consumption has been reduced to less than 3.0 kghg phenol. The quantity and total BOD of aqueous effluent are minimal as are the total VOC from

Commodal Installatlonr: More than 50% of the world’s phenol capacity is based on this technology, including the largest and most efficient single train fidlitics. Capadties range fmm 50,000 tpy KO 270,000 tpy. Uconsor: The M.W. Kellogg Co.

the plant.

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Alkylbenzene, linear Appleation: To produce linear alkylbenzene (LAB) from C,o to C,, linear pardYms by alkylating benzene with olefins made by the P a d dehydrogenation and the DeFine selective hydrogenation procuscs. The alkylation reaction is camed out over a solid, heterogeneous catalyst in the Detal process unit. Descrlptfoffi The Pad reactor (1) dehydrogenates the feed to the corresponding lhur olefin. The reactor effluent is separated into gas and liquid p k in a separator (2). Diolefins in the Pacol separator liquid ue relmively converted back to mono-olefins in the &Fine reactor (3). Light ends are removed from the reactor effluent in a stripper (4). The olefin-paraffin mixture then alky- lates with benzene in the fixed-bed Detal reactor (5). T h e product from the reactor flows to the fractionation section (6) for separation and m y d e of unrcacted benzene to the reactor. Unrcacted paraffins are separated (7) and recycled to the Pacol section. A rerun column (8) separates the LAB product from the heavy alky- late bottoms stream.

The protxss is nmpoiluting, no process waste streams arc produced. The catalysts used arc noncorrosive and require no special handling. Welds Based on 100 might units of LAB, 76 units of linear par- a n t and 33 units of benzene arc charged to the process. The LAB product has a typical Bromine Index of less than 15 and is 99% sulfonable. Economla U.S. Gulf Coast battery limits estimated erected cost based on producing 50,000 tpy of LAB.

Investment, Wpy 680

c a t a l y S t a n d c h e ~ , S 36 b, k W h 182 Water, coding. m‘ 320 Fuel fired, lff keal 4.0

Typical utllitia tonsumption per ton of LAB:

Commercial plants Nineteen Pacol-based LAB complexes arc in operation, with eight more in design or construction. One complex with the Detal pmcat is in design. Roforonco: B. V. Von, et. d., “Recent Advances in the Produc- tion of Detergent Olefms and Lmcar Alkylbenzene,” Society of Chemical Industry, University of Cambridge, England, March 1990.

Ucenson UOP (the Detal process is jointly licensed with CEPSA).

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130 Hydrocarbon Processing, March 1991


Aromatics Application: To selectively convert toluene to high-purity benzene and a unique xylene product with a para-xylene content of up to 95%, which significantly exceeds equilibrium concentration, using the Mobil Selective Toluene Disproportionation (MSTDP) process. De8cdptlon: Dry toluene feed and hydrogen-rich recycle arc pumped through feed effluent heat exchangvs and the charge heater into the MSTDP reactor (I). The vapor then flows down through the fixed bed of MSTDP catalyst. Toluene disproportionation occurs in vapor phase in rhe MSTDP reactor at elevated :mperature to produce benzene and the para-rich xylene prod- ct. T h e reactor effluent is cooled by heat exchange with the liq-

uid feed and the resulting liquid and vapor phases are separated (2). Hydrogen-rich vapor phase is recycled back to the reactor charge together with make-up hydrogen. Separator liquid is first stripped of dissolved gaseous p r o d u c ~ in the stabilizer (3) and then fractionated in the light aromatics tower to separate the benzene and xylene products from unconverted toluene and a mall quantity of heavy aromatic material. Unconverted toluene i s re cyded to extinction. Yleldr, wt% from MSTDP ~ c t o r :

Ftbd Pmdud C, & lighter 1.8 Benzene 13.9 Toluene 100.0 70.0 Ethylbenzene 0.6

11.4 1.4

P W e M tTkX*fW 0-Xylene 0 3

0.6 Cr i Aromatics 100.0 100.0

Toluene conversion, wt% 30.0 87.0

- - pxylene in xylene fraction, %

Operatlng condltlon.: Temperature, pressure and space veloc- ity arc moderate and the hydrogen to toluene mole ratio b low.

T h e key to the MSTDP pmccss is the synergistic combination of a proprietary Mobil catalyst and a novel prctruunent procc- dure that selectivates the catalyn at the beginning of ucb cyde.

Economics: Estimated on-sit? battery limit investment for 1993 open-shop construction at U.S. Gulf Coast Iocation, $2,165 per bpsd capacity. The 87 + % para-enriched xylene product rcduca capital and operating costs of either adsorption or crystallization mcovery processes which produce savings of 20-50% in MSTDP processing costs. Commorchi piants: Three companies have licenscd the pro-

Roforonco: American Chemical Society Acs s p p . Ser. No. 248 (1984).

Uconmor: Mobil Oil Corp.

cas .

Benzene Appllcatlont To produce high-purity benzene and heavier ammatics from toluene and heavier ammatics using the Detol pro-

D~scdptlom Feed and hydrogen 11c heated and parsed wer the catalyst (1). Benzene and unconverted toluene andlor xylene and heavier aromatics arc condensed (2) and stabilized (3).

To meet acid wash color specifications, stabilizer bottoms arc passed through a frxed bed clay treater, then distilled (4) to produce the desired specification benzene.

Unconverted toluene andlor xylenu and heavier aromatics are recycled. Yleldr: Aromatic yield is 99.0 mol% of fresh toluene or heavier aromatic charge. Typical yields for production of benzene and xylenes arc: Xylene

cess.

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Type production Benzene

Nonaromatics 3.2 2.3 Benzene - 11.3 Toluene 47.3 0.7 C, Aromatics 49.5 0.3

Benzene’ 75.7 36.9 - 37.7 C, Aromatics“ 5.45% mu” (mu. panl

F e d , wt%

C,* Aromatics 85.4 Products, wt% of feed

.- 1.OoDprn - “urr)

Economics8 Basis of 100-million-gpy: Investment, SlbW 2.650

Electricity. kWh 5.8

Water, cooling. gal 450 Steam, Ib 14.4

Typical uUllty requirements, per bbl feed:

Fuel, MMBtu 0.31

* No cndn w o n far u m grr at”

Commorclal plantr: Twelve plants with capacities ‘Mging from about 12 million to 100 million gallons per year have been licenscd. Uconmor: ABB Lummus Crest, Inc.

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Hydro&rbon Processing, March 1991 141


1 C v ” PoQua I

Cumene Appnutlon: To produce cumene (isopropylbenzene) by alkylating benzene with propylene. The technology can process a wide range of propylene purities and typical extraction-grade benzene.

De8crlptlon: Fresh propylene feed h combined with fnsh plus rtcycled benzene and is passed through heat exchange and a hot oil or num prtheater before bung charged to the reactor (1). The reactor effluent is routed to a two-stage flash system (2-3) that also includes a depropanizing rectifying section (4). Much of the benzene recycle is sepamted in this flash system. The benzene feedstock is fed to the depropanizing d f i e r (4). The enriched cumene stream is then fed to the benzene column (5). where the remainder of the benzene recycle is separated. The cumene is then clay treated (6) prior to final fractionation (7) to remove a small quantity of heavier material, produced primarily from side reactions in the alkylation reactor. The bottoms from this final fractionator is a highly aromatic material containing mainly diiso- propylbenzene (DIPB). The DIPB is reacted back to cumene in the uansalkyladon section of the unit (8).

Yieldr: B a d on 100 weight units of cumene produced, approximately 66 units of benzene and 36.5 units of propylene arc charged to the unit. The cumene product is at least 99 % purc and m m s all requirements for phenol production. Etonomlcs: Based on a unit produang 100,000 tpy of cumene located in the U.S. Gulf Coast area. The investment covers inside the proccss area battery limits.

Investment. $/tpy 146 Typical utilfties consumption

per metric ton of cumene: CaWyst and chemicals. S 6.1 Power. k w h 25 Steam, ton - 0.17 Fuel fired, 1V kcal 0.24 Water. coding. d 13

Commercid Status: The process is used for the production of 90% of the world’s open-market cumene supply. Ucensor: UOP.

I Fuel, p u

1 Purge gas

Cyclohexane AppIiutloffi To produce high-purity cyclohexane from benzene using liquid-phase catalytic hydrogenation. De.ulptlon: Hydrogenation is almost completely achieved in the liquid-phax reactor (1) when the catalyst is kept in suspension by an external pumparound. Heat in excess is removed in an exchanger where low-prruurc steam h produced (2). A small catalytic pot (3) acts as finishing reactor when the conversion of the main reactor drops below the required level either acciden- d l y or when the catalyst has to be changed.

After condensation, the reactor effluent is flashed in a high- pressure separator (4). A stabilizer (5 ) removes hydrogen and other light dissolved gases.

Depending on hydrogen-rich gas composition and price, flashed gas from the separator may be recycled to the main reactor in order to obtain a better use of the hydrogen feed.

Practically stoichiometric yields of cyclohexane from benzene are obtained. The purity of the cyclohexane product depends on the purity of the benzene feed. Economic.: Bash of 100,000 tpy, erected battery limits, engineering excluded, France 1991:

Investment (feed dryer included), SRpy Catalyst initial load, S s1oo,oO0

40

Catalyst consumption. Sn 2.5 Typical requirements using 95% purity Ha. per ton of cycle-

tmxane produced: aectricii. Icw 15 Steam. MI? kg 90 Steam, Lp. kg 53 Water, cooling (dT = 10%). t Chilling (pmcess side outlet 1 5 O C ) .

kcal 380

6.2

Commerelal plant.: Total of 23 plants representing 1.8 million tpy use this technology. Uconsor: Institut F r a n e du Pitrole.

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Petrochemical Handbook '91

Proaucr r-0- To wane

Dimethyl formamide Application: To produce dimethyl formunick from dimethyl- amine (DMA) and urbon monoxide (CO).

Descrlption: In thii process, carbon monoxide and dimethyl- amine are reacted in the presence of a atalyn and solvent at high pressure and moderate temperatures in a specialized reactor (1) to produce dimethyl formamide. The mactor elf)uent is then distilled (3, 4) to produce dimethyl formamide. which is further purified (5) to produce high uality solvent and fibergrade product. Solvent and excess dime%ylamine arc fed back to the reactor. Catalyst is removed continuously from the system. Utility consumptlons: Typical per 100 Ib of product: .

Steam. Ib 85 Water, cooling, gal 1.500 '

Electricity, kWh 2

Yields: CO yield depends on concentration, and concentrations as low as 25% CO can be used. DMA yield 95%.

Product speciflcatlons:

Color, Alpha, max. 5 Alkalinity, ppm 1" Acidity, ppm Traw HzO, PPm . 200 pH (in HnO soin.) 6.7-7.3 Purity. % 99.99

Commercial plants: Nissan Chemid , ICI; Celancle Mex- icana; Korea Fertilizer Co; Japan Cas Chunicrl (now Miuu- bishi); Lee Chang Yung Chemiul; Rashuiya Chaniuls and Fu- tilizers; Ak-Kim AS., Dong Feng Chcmid . Ucenson Acid-Amine Tcchnologicl, Inc

PEB recycle r 1

Recycle ~nuw I Ethylwnrcm

Benzene f I

Et hylbenzene Appllcatlon: To produce ethylbcnrene (EB) by alkylation of benzene with ethylene in the vapor phase, usbg a fwed-bed reactor. Descrlptlon: Ethylene feedstocks as low as 10 mol % purity (such as FCC offgas) can be used economically. The product EB is suitable for making styrene monomer by all known process routes. Additional economies are possible by a union of thii EB process with a companion styrene process.

In the reaction section (I) fresh and recycle benzene are vapor- ized and preheated and then combined with a polyethylbenzene (PEB) recycle stream and fresh ethylene and fed to a reactor containing a proprietary, fixed bed heterogeneous catalyst developed by Mobil. The benzene is alkylated with ethylene in the vapor phase at moderate pressure. The reactor efnuent is fed to the benzene fractionation system (2) for recovery of unrcacted benzene for recycle to the reactor. The remainder of thc reactor effluent is fractionated in a two-column system. In the EB recovery column (3) EB product is separated from higher boiling components. The bottoms from the EB recovery column are further distilled in the PEB recovery column (4). PEE and other alkylaromatics are recovered overhead and recycled to the reaction smion. A small midue stream from the bottom of the column can be used as fuel.

The process i s highly energy efficient: essentially all of the process heat input plus heat of reaction can be recovered as useful medium- and low-pressure steam. Design flexibility allows the use of alternative heating medir: steam, hot oil or direct fired re- boilen.

hvironmentally, the proarr is nonpolluting; no process waste streams are produced. The au lys t is noncorrosive, nonhuar- dour, environmentalIy inert and requires no special handing. Materials of construction are p e r a l l y carbon sted throughout. Economics: The process &eves near stoichiometric yields at very high energy efficiency.

Utility data per kllogmm of product Net energy export. kcal 200 Catalyst and chemicals, US.$ 0.0005

~mmercia l plantrt The pmceu has been selected for use in 21 units (including four using dilute ethylene feedstock) ranging in size from about 20,000 to over 800,000 metric-tpy. The aggregate capacity of such units exceeds 6 million metric-tpy of EB since the process was commercialized in 1980.

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Ucensor: The Badger Co., Inc.

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154 Hvdrocarbon Processing, March 1991


M.*h JnnYalld8

H

Maleic anhydride Applteatlon: To produce maleic anhydride (MA) from normal butane and air via gas phase catalytic oxidation.

Descrlptlon: Butane is the preferred feedstock for MA because of environmental and economic considerations. Normal butane and air arc fed to a multitube fixed bed reactor (1) that is cooled with molten salt. MA is produced in the presence of a proprietary modified vanadium oxide catalyst. The uriting gas stream is cooled and crude MA is nearly quantitatively absorbed in an absorber (2) using a rtadily available solvent. Crude MA, sufficiently pure for many applications, is removed from the solvent in a stripper (3). The crude MA can be further purified in a batch distillation column (4). A portion of the recycled solvent is sent to a proprietary solvent purification system (5) to minimize buildup of high-boiling impurities. The continuous, patented recovery system has several advantages over aqueous recovery: a) drastically lower aqueous waste discharges; b) lower energy consumption; c) higher onstream time because of the absence of insoluble furnaric acid that can foul equipment; and d) higher recovery of crude maleic.

Mter removal of MA, the reactor offgas, containing significant fuel value, is sent to an incinerator or other disposal equipment. Byprodua steam is produced in the reactor from the urorhennic reaction and in the gas cooler by cooling the offgas. Additional steam can be generated from burning the offgas. Economics: Economical use of byproduct steam is a key to low cost. The process can be adapted to maximum steam utpon or zero steam export. Economic evaluation data arc available for spedfz situations. Commmlal plant.: Monsanto has used this technology s i n a 1983 in the wodd's largest M A plant (1 09,OOO metric tpy) in Pen- sacda, F k The fint license of the technology was to Union Pet- rochemid Corp.'s 20,000. tpy plant in Taiwan starting up in late 1990.

Refaronce: Burnett, J. C., Keppel, R. A. and Robinson, W. D., Ckdpis Tdag, Vol. 1, No. 5, October 1987, pp. 537-586.

Ucclruon Monsanto Co.

Methanol Applktion: The IC1 Low Pressure Methanol Process produces dd methanol of high puriry. The prinapal feedstock used is M I U ~ gas. although naphtha, heavier oil fractions or coal are rko wd. Dmscdption: The methanol process can be divided into thrce main sections, (I) synthesis preparation, (11) methanol rynthe-

covey and recycle streams, there is considerable interaction between the three.

O.Synthesis gas is most commonly produced by the steam re- formng of natural gas. The gas is first desulfurized (1) and then passed to a saturator (2) in which roccss condensate is evapora-

the combined gases reacted over a nickel catalyst in the reforming furnace. The resulting synthesis gas, containing a mixture of hy- dmgat, carbon oxides, steam and residual methane leaves the r e farma at about 88OOC and 20 bar, and is cooled before Wig c a m p d to synthesis prrtrurc.

(II)The synthesis loop comprises a armlator (3). convener (4). f d d u e n t exchanger, heat rccwuy exchangers and separator (5). For large plants, loop opvlting pressure is in the ran e 80- 100 bat The convener contains a copper based catalyst anbopcr- ua in the range 240-27OoC. Thc reaction is limited by equilibrium and the methanol con-

centration at the convener exit ' ve ly exceeds 7 %. The converter effluent is cooled to 40OC to condense product methanol, and the u n r a a d gases arc myded to the circulator. A purge is taken from the recycle gas to remove inerts such as nitrogen, argon mnhuK and surplus hydrogen. This k used as fuel in the re- fonnu @I) Crude methanol from the separator contains water and

low l m k of byproducts, which M removed using a two column dinilktion system. The fint column (6) nmova light ends such as ethers. esters acctene and lower hydrocarbons. T h e second (7) remove3 water, higher alcohols and higher hydrocarbons. Economics: Production costs arc dominated by natural gas cost md capital charges. The feedstock and fuel requirements arc 7.0- 7.8 GaUmetric ton of methanol (28-31 MMBtdmcuic ton). Capital cost clll vary considerably depending on location and avlikMe infnstructurc. A guideline figure for a 2,000 ton per day phot is U.S. $250-300 million. Comnurtlrl plantst 44 methanol plants have been built using the IC1 process. Four plants arc presently under construction. Uc~nror: IC1 Katalco.

bs and 011) methanol pun ip" ication. Because of extensive hear rc-

ted to produce process steam. Fur t! er process steam is added and

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Polycaproamide Appllc8tion: To produce polycaproamide (Nylon 6) chips by po- lymerizing caprolactam monomer using EMS-lnventa's VK-tube method. Description: In the presence of water, stabilizers and modifying additives (l), caprolactam monomer is continuously polymerized (2, 3). Prepolymerization is available for large units to reduce reactor volumes and improve product qu&ty.

The raw polymer melt is extruded (4) into strands and cut into granules. These chips (5 ) contain approximately 8% of monomers and oligomers which 3re removed by hot water in an extraction column (6). After dewatering of the extracted chips they M dried in a two-stage column system (7.8, 9) by hot and dry nitrogen.

The relative viscosity of the final chips can be varied according to requirements from 2.5 through 3.4 and up to 7.0 when solid- state post condensation conditions are applied to the drying stage.

A variety of recovery process routes for the recyling of cxtracta- bles (monomer and oligomers) from polymerization and polymer waste from rurrile sections help to cut raw material cosu.

Chips from the above mentioned process are a successful feedstock for the application in all textile processes, especially the new single-stage H I S process for the manufacture of flat textile filament yam developed by EMS-Invent. &.

Batch and continuous process steps M available to fit all requirements regarding polymer grader. flexibility of output and plant size. Special effons arc given to the plant design to achieve lowest material, energy and personnel costs.

Commerclal plantu More than 20 plana arc in operation or under construction in Argentina, Australia, Belgium, Brazil, Co- lombia, Great Britain, India, I d y , Japan, South Korea; P A - stan, P.R. China, Philippines, Romania, Switzerland, Taiwan. Thailand, U.S. and Yugoslavia Ucensor: EMS-Invenu AG.

m

Pol yet hylene AppllC8tlOn: Produce linear polyethylene (LPE) using the Phil- lips Petroleum Co. LPE Pmcess. Descrlption: Polyethylene resins ranging in melt indices from leu than 2 HLMI IO greater than 200 MI, densities from slighrly Ius than 0.920 to 0.970 grlcc, and molecular weight distribution from very narrow IO very broad are produced by the Phillips LPE Process. Polymerization occurs in an isobutane slurry using very high activity proprietary catalysu (1) in a loop reactor (2). Melt index and molecular weight distribution are controlled by catalyst, operating conditions and hydrogen. Density is controlled by comonomer incorporation (3). Comonomers that can be used indude butene-1, hexene-I, 4-methyl-1, pentene and octene-I. "he high activity catalysts used eliminate the need for catalyst removal. No waxes or other byproduas are formed during polymerization thereby minimizing environmental emissions.

Ethylene, isobutane, comonomer and catalyst are continuously fed to the loop reactor where polymerization occurs at tempera- tum lower than 100°C and pressures of approximately 40 kg/un2 and residence t ima of approximately one hour. Ethylene conversion arceeds 97% per pass (4). The reactor effluent is flashed KO separate the solid ruin from the gaseous stream (5). Polyethylene powder is purg#l(6) with nitrogen to remove traces of hydrocarbons and pneumatically conveyed to the extrusion area (7) for stabilkation and pelletizing. The gaseous stream is compressed (8,9), purified and recycled back to the reactor. Product.: Homopolymers and copolymers arc produced for ap- ~ l iu t ions in film, blow molding, injection molding, roto mold- mg, pipe, sheet and thermoforming, and wire and cable. R m matorlais 8nd utlIftles: The consumptions shown below M per metric ton of pelleted min and representative of condi- tionr for both homopolymer and copolymer production.

Catatyst and chemicals, U.S.S. 2.00-1 0.00 Steam, metric ton 0.25 Electricity, kWh 350 Water, cooling (circulating). metric ton Nitrogen. Nm) 50

. , ,

Ethylene, metric ton 1.007

185

'D.pWonP"sma ~

Commercial plants: Seventy-scven reactor lines arc either in operation or construction worldwide and account for 34% of worldwide capacity. Ucensor: Phillips Petroleum Company.

.:. .

-16-

170 Hydrocarbon Processing. March 1391


Polypropylene ApplIutIon: To produce homopolymer, random copolymer and impact copolymer polypropylene using the Union CarbiddShell Oil (USA) gas-phase Unipol PP process.

Do.erlption: A wide range of polypropylene is made in a gas- phase, fluidized-bed reactor using proprietary catalysts. Melt index, atactic level and molecular weight distribution arc conwlled by selecting the proper catalyst. adjusting operating conditions and adding molecular weight control agents. Random copolymers arc produced by adding ethylene to the reactor. Ethylene addition to the second reactor in series is used to produce the rubber phase of impact copolymers.

The simple and direct nature of the Unipol process results in low levels of environmental pollution, minimizes potential fire and explosion hazards and makes the process easy to operate and maintain.

To produce homopolymers and random copolymers, gaseous pmpylene, comonomer and catalyst arc fed to a reactor (1) containing a fluidized-bed of growing polymer parrider and operat- k g near 35 kg/cm2 and approximately 7OOC. A conventional, single-stage, centrifugal compressor (2) arculates the reaction gas which fluidizes the rucrion bed and provides raw materials for the polymerization reaction, and removes the h u t of the d o n from the bed. The circulating gas is cooled in a conventional h u t exchanger (3). The ular product flows intermittently into product discharge tanG) wherc unrcacted gas is separated from the product and returned to the reactor. To produce impact copolymers, the polypropylene resin formed

in the first reactor (1) is arnsfcmd into the impaa ructor (5). Gaseous propylene and ethylene arc fed into the impact reactor to produce the polymeric rubber phase. The impact reactor opurtes in the same m m e r as the initial reactor, but at approximately onehalf the pressure, with a centrifugal compressor (6) circulating gas through a h u t utdangcr (7) and back to the fluid-bed reactor. Impact copolymer is removed by product discharge tanks (8) and u m e d gas is murned to the reactor. In both wet hydrocarbons remaining in the product arc n-

moved by purging with nitrogen. The granular products arc subsequently pelletized in a pro rietary low-encrgy system. Con- trolled rheology, high melt ;ow grades a n produced in the pdledng system through the addition of relccted peroxides. Prod-: Homopolymen can be produced with melt flows from leu than 0.1 to 3000 and isotactic content up to 99%. Random copolymers un be produced with up to 12% ethylene over a wide melt flow range (CO.1 to > 100). A full m g e of impact copoly- men can be wlvmerized with a good stiffness to imoact balance.

Polystyrene Apptkatlon: To produce expandable polystyrene via the suspension process using Huntsman Chemical CorporatiodLummus Crest Inc. technology. Doscrlptlon: The HCCLCI styrene polymerization technology for the manufacture of expandable polystyrene (EPS) is a batch suspension followed by continuous dewatering, drying and size darr;ifrcation.

B a d on the formulation, monomer, water, initiators, suspending agents and other minor ingredients arc added to the reactor (I). The contents are then subjected to a time-temperature profile under agitation. The suspending agent and agitation disperse the monomer to form beads. At the appropriate time a premeasured quantity of pentane is introduced into the reactor. Polymerization is then continued to essentially 100% conversion. After coaling, the polystyrene beads and water are discharged to a holding tank (2). From this point, the process becomes continuous. The bead/

water slurry is ccnvifugcd (3) where most of the “mother liquor” i s ranwed. The beads w conveyed to a pneumatic dryer (4) where the remaining moisture h removed.

The dry be& arc then pncumatiully conveyed to condition- ing unks (5) of proprietary design. The conditioned beads are then vmnd (6) to as many as four products cuts. External lubri- a n t s arc added and blended (7) and (8) and the finished product is conveyed to shipping containers (9). Raw m8terials 8nd utllltlo~: Based on one metric ton of ex-

.

pandable polyrtyrrne:

Slyreno and pentane, kg 1.028 Prooess chemicals, kg 10-14

1 ,OOo Dminenlisd Ha, kg EkWkiity. k w h 176

1.8 5.2

Steam, tons Wuc cooling, ni‘

##~tdhuOn8S Thm commercial production units are in operation: two in the United States and one in Quebec, Canada, for a t o d capacity of 70,000 metric tons. Economle.: The HCCLCI process offers one of the most mod- e m tahnologier for expandable polystyrene production. Com- puter control is used to produce product uniformity while minimizing plant energy requirements. HuntsmadLC1 technology provides ongoing research of the process for product improvement and new product potential.

. Uconson Lummus Crest Inc. ?roducu froB narrow IO broad ~olccular weight diskbution CM ._ be manufactured.

Commercial plantst Twenty reaction lines arc in operation, under construction or in design phase worldwide with single line ca- - 1 7 - paciaa ranging from 80,000 to 200,000 tons-per-year. U~mror: Union Carbide Chemicals and Plastics Company Inc. 176 Hydrocarbon Proceuing, March 1991

. .

.. . . : . . . ,.. . . ,. . ... .

..


11 PVC (emulsion) Appllcatlon: A process to produce emulsion polyvinyl chloride from vinyl chloride monomer (VCM) using special emulsifiers, catalysu and additives. Descrlptlon: The process has great versatility and high productivity. With the same equipment, t h m different types of emulsion resins can be produced using different techniques: seeded, un- seeded, and blended emulsions. to give mono or multimodal dic- tributions merely by varying operating conditions and recipes. The use of reflux condensers (1) with an effective buildup sup pressant and of well established recipes results in a productivity of up to 350 tonslyr per m' of reactor volume. The proprietary 'wildup sup ressant, in particular, makes possible hundreds of onsecutive gatchu with only a low-pressure rinse between bat-

ches. Catalysts, emulsifiers, and other additives are prepared in mix

tanks (2). Once the reactor (3) is charged with VCM and water, the polymerization is carried out batchwise, under controlled temperature conditions. By a combination of agitation and em& sifier agents, solid PVC panicles arc formed and anukified in water. Particle site of the polymer pmduct is controlled by uiing a proper combination of reaction conditions and emulsifiers.

Following polymerization, the latex is run down into a buffer vessel (4). and then it is fed to continuous VCM stripping (5) where VCM is removed and sent for recovery. Residual VCM in the PVC resin is Ius than one ppm. After suipping, the htac i s pumped to the main latex storage (6), and then to the spray dryer (7). k t u r is dried with heated air to remove water. The fine dered resin is separated from the dryer exhaust in a filter (r

The powder passes continuously to a surge hopper (9). tbrargb a screening stage (1 0). and then into the milling d o n (1 I). The product flows to a surge tank mounted above a bagging machine (12). E c o n o m I CII

Raw materials and utllltiet, per ton of PVC VCM. tons 1 .w Electricity. kwh 350 Steam (6 ka/cm). kg 500 Natural gas, d 90

Deionized water. d 2 Chilled water (15. C), d 1 50

Commorclal plant.: EVC has 5 plants in Western Europe. Present production is 120,000 tondyr. kensor: European Vinyls Corporation (Americas), Inc


h

PVC (suspension) Appllutlon: A process to produn polyvinyl chloride (PVC) from vinyl chloride monomer (VCM) using suspension polymerization. Doscriptlon: PVC is produced by batch polymerization of VCM dispersed in water. This is a f m d c a l aothermic reaction carried out in a stirred reactor. Reactor sizes range from 20-105 m'. The choice will depend on capacity and the number of gdu required. Process control can vary from manual opvltion to a complete supervisory computer system.

The reactor (1) is charged with water, additives and VCM. The reaction is controlled at a temperature between 53°C and 70°C to give a polymer of a particular molecular weight. The reaction is dlowui to go to a conversion (85 to 94%) appropriate to the p d e . The heat of reaction is removed by cooling water in the jacket and, in the case of larger reactors, by reflux Condensers as well. At the end of the reaction, the PVC and water, in the form of a durry, are run down to a blowdown vessel (2) from which art of the u n ~ c t e d monomer flashes off to be recovered (4). he m r i n i n g VCM is moved in a continuous stripping col-

umn (3) with s t u m . The proprietary design of the column offers low steam consumption, mini& product degradation and vir- tually eliminates the requirement for periodic cleaning. After stripping, the slurry is centrihrged (5) and dried (6). Residual VCM is less than one ppm in the ruin.

Ruin deposits in the reactor arc pmentcd by the use of a proprietary buildup suppressant which is applied before every batch. After rundown, a low prusurc rinse with water is Chat is needed to remove loose polymer and the cycle is ready to restart. The reactor only needs to be opened for thorough cleaning after 500 or more batches.

Economieu

Raw materirb and utllltles, per ton of PVC VCM. tons 1.004 Ekctricity. kwh 200 . SOU^, 6.5 kglcm% tons 0.9 Water, cooling (5. C rise). d Demin wafer, m' 2 2 Process water. d 1 .s

05

Wntenance, per yr as % of investment 2

Commorclal plants: EVC opentes eight suspension PVC planu Total innalled capacity is about 1,000,000 tondyr. The process has been licensed four times.

Uconsor. European Vinyls Corporation (Americas), Inc.

. . . .. .

. . .. . . . . .. . .

... .'

-18-


Styrene Appllcatlon: To produce polymer-grade styrrne monomer by alkylating benzene with ethylene to form ethylbenzene, which is d e hydrogenated to styrene.

Doscriptlon: The alkylation, with benzene in ~ ( c u s from the benzene drying column (1). cakes place in a homogeneous system (2) using aluminum chloride catalyst. Catalyst is continuously removed (3) and replenished. Removed catalyst u convured to aqueous aluminum chloride solution as a byproduct +itable for water and paper making treatment applications. A fractionation system (4 , 5 , 6) recovCrS high purity ethylbenzene. Polyethylben- zenes and unconverted benzene are recycled. The heavy residue, flux oil, is used for fuel oil.

Ethylbenzene dehydrogenation (7) also is catalytic, using commercially available catalyst with about M O years' life. An innova- tive reactor design provides high thermal efficiency and excellent mechanical reliability. Process condensace from the dchydrogcna- tions step is stripped (8) to remove dissolved u~matiu and is used inside the unit as boiler feed water. A frrcdonadon Vrin (9. 10) separates high-purity styrene. Unconverted ethylbenzene, and the relatively minor reaction byproducts. Toluene is produced as a minor byproduct (1 1 , 12).

Oporating condltlonsr T h e alkylation step operates efiaendy at low bcnrene-to-ethylene ratios, resulting in low associated processing cosu. Heat of reaction is recovered as steam that can be internally utilized.

The dehydrogenation step is k e d out in the presence of steam at high temperature under vacuum. The conditions am set for optimum attainment of yields and conversions. Styrene distillation is carried out in the presence of a proprietary non-sulfur polymerization inhibitor. OpontJng data: F e d , kglkg monomer

Ethylene 0280

Catalyst and chemicalq, Clkg 0.650

Benzene 0.776 UUlily consumption, kcykg 1,370

Note: Feed and utility requirements rrxnced arc resentative; t h y would be optimized for spccilc mw m a t m T a n d utility availability and cost conditions. This includes the most up-to-date commercially proven and patented system for recovering about 500 kcal low-level energy per kg of styrene pmduced, without rcquiring any compression equipment. Commorclal piants: Twenty operating planu incorpome fu-

of the latest generation MonsantdLummus Crest tcchnol- m. Thac units, louted in various pans of the world, account for

Over 3.6 MMtpy of styrene capacity. Their individual capacities M g e from 60,000 to 680,OOO tpy.

1

. . :- I . .

Suif onation AppaUtIom To produce sulfates and sulfonates of detergent al- kylates, fatty alcohols, ethoxylated alcohols, alpha-olefins, ctc., wing SO, in a continuous muldtube, film reaction. Doserfptlonr The Ballcstm multitube film reactor giva top- quality sulfonated producu over the whole rangc of sulfonated anionic surfactants. including the traditional akylantene and the recently developed a lpha-o ld i and methylester-sulfonates.

The raw materid combines with SO, in the f - reactor (1 . The product then p e s to an ageing (2) and a stabilizing unit ( 3 ) and double-step neutralization (4, 5). Alpha olefins hydrolysis (6) is located between the M O neutralization steps. OK gases pass to an elcnronatic pmcipitator (7) and scrubber column (8).

.A great variety of products IS obtainable from a small number of basic sulf(on)ated products neutralized subsequently with different bases, diluted to different concentrations, with addition of inorganic salts, thickening agents, brighteners, opacircn, pre- serving agents and other builders. Economlcu For the production of 3,000 kg/b of 100% active muter, the estimated investment for a skid-mounted plant will be: U.S. SI .93 million (production of gaseous SO, included, par- t i d y skid-mounted and/or prefabricated). Raw matorlds and utlllty consumptlonrr per feed:

WaIyst.Ibpr1 I b f d Sulfur, b per ton feed Process water, gal Ware cooling (9.F rise). gal st- (57 prig), m EbUrW. kwh Maintenance, per yr as % of investment

metric ton

negligible 41 3

1130

5

8.000 . in .

Commorclal plant.: There arc more than 100 industrial planu installed throughout the world with the film sulfonation system.

Roforoncor Morctti, G.E and Adami, I., "Sulphonation of Ethoxyiatcd Alcohols in Multitube Film Reactor: Product Qual- ity and Reaction Con& for Low Dioxane Content," CESIO Congress, 1988.

Ucoruon Ballutra SPA.

Uconsorsr Monsanto Co. and ABB Lummus Crest, Inc. -19-



. From the process flow diagrams, it is interesting to note the wide variety of processes

that exist in the chemical industry.

ACTIVITY 2 Process Characterization

OBJECTIVE : To become familiar with process characterization terminology

including: Production units, units of product, byproducts, and

emissions as they apply to the chemical industry.

With the process flow diagrams identified in Facility A and B, list

the units of product, products, production units, byproducts and

emissions for each facility.

TASK 1:

FACILITY A:

Facility A has an ethyl benzene, styrene and polystyrene process.

the polystyrene process are closed loop returned into the distillation process of the

styrene unit.

Byproducts from

FACILITY B:

Facility B has an ethyl benzene, toluene, and polystyrene process.

-20-


PRODUCTS

FACILITY A

ACTIVITY 2 WORKSHEET

PRODUCTION UNITS UNITS OF PRODUCT BYF'RODUCTS EMISSIONS

-21-

CHEMICAL AND POLYMER INDUSTRY MODULE -~ -

FACILITY B

ACTIVITY 2 WORKSHEET

PRODUCTS PRODUCTION UNITS UNITS OF PRODUCT

-22-

BYPRODUCTS EMISSIONS __ __

CHEMICALAND POLYMER INDUSTRY MODULE

TASK 2: If information for your worksheet is lacking from the process flow

diagrams, determine what data your TURplanning team would

need to evaluate in order to complete your work sheets.

DATATO EVALUATE

FACILITY A

FACILITY B


3.0 TOXIC USE REDUCTION OPTIONS

At the end of this section participants willbe able to:

. Understand toxic use reduction options available within the

chemical industry.

. Develop toxic use reduction options within industry specific

areas.

The Toxic Use Reduction Law identifies six toxic use reduction techniques by name.

These techniques include:

Input substitution

Product reformulation

Production unit redesign

Production unit modernization

Improved operations and maintenance of production

Recycling or reuse

Each technique must be evaluated with a production unit as a potential option ifthe

technique reduces the amounts of toxics being used. The option must then have a

-24 -


impact assessment

feasibility being technical and economic, other factors such as acceptance at all levels

within a company, effects on health and safety and the environment, and community

concerns willaffect an options potential for success.

completed to determine feasibility. Although the main criteria for

4

The option evaluated should be included in the TURplan. The implementation and

monitoring of the plan willbe critical for the option and the plans success.

ACTIVITY1 Screening Options

OBJECTIVE: To understand and screen toxic use reduction options within

specific industry areas.

TASK 1 : Using the options generated below, determine ifthey meet the

definition of toxic use reduction and determine the TUR technique

involved.

-25-


ODtion - Generated Meets TUR(Y/N) TUR Techniaue

Generated Options

.

Recycle process byproducts back into the process in an open system.

Convert CFC's to helium for refrigerated systems

Convert use of methylene chloride solvents to N-methyl-2 pyrrolidone in

process cleaning.

Replace "Leaky seals" in a process with a more chemically resistant seals or

mechanical seals.

Institute a waste watcher team that inspects and repairs leaking flanges,

valves, and seals routinely.

Install a closed loop recycling system for your production process

Distilland reuse solvents.

-26-


. Install a chemical on demand process system to replace the purchase and

use of certain listed chemicals.

. Install interlock hose lines to eliminate spillage at loading and unloading

areas.

. Implement a new inventory control system.

Update operating procedures to minimize environmental losses.

Incineration of byproduct waste streams for process energy recovery.

Recycle, distill and reuse spent waste water.

. Install conservation recovery vents on storage tanks

Redesign facilityprocess piping to eliminate valves, flanges and seals

wherever possible with welded pipes.

. Install a super critical fluid extraction system based on CO, to replace

solvents use.

ACTIVITY2 TURGoals and Objectives

OBJECTIVE : Develop toxic use reduction gods and objectives

TASK 1: Based on the valid options listed in Activity 1, determine what option impact

assessment criteria would be used and rank the options.

TASK 2: Identify your objectives for short and long term planning.

-27-

CHEMICAL AND POLYMER INDUSTRY MODULE -- ~

Options . Now - 6 months 2 vears

-2a-


4.0 TOXIC USE REDUCTION PLANNING PROCESS GUIDELINES

The following guidelines are presented as a tool for reviewing Toxic Use Reduction

Plans and the planning process within organizations.

-29-


TUR PLANNINGPROCESS GUIDELINES - Randy Morris

A Identification and Evaluation

1 .o Materials and Processes Evaluated

1.1 Materials: Listed/Used

1.2 Storage

1.3 Disposed

1.4 Accounting

1.5 Units of Product

1.6 Production Units

1.7 Processes

1.8 Process Flow

1.9 Emissions

2.0 Byproducts

2.1 Process Products

2.2 Base Year Byproducts Index

2.3 Base Year Emissions Index

2.4 Current Year Byproducts Index

2.5 Current Year Emissions Index

2.6 Toxic Reduction Opportunities

-30-

CHEMICALAND POLYMERINDUSTRYMODULE ~~

2.7 TUR OptiondTechniques

2.7.1 TUR Reduction Analysis

2.7.2 Financial Analysis

B Development of the Plan

1 .o

1.1

1.2

1.2a

1.2b

1.3

1.4

1.5

2.0

2.1

2.2

2.3

3.0

3.1

3.2

3.3

3.4

Policy Statement

Goals

Objectives

2 Year Goal

5 Year Goal

Signed by Management

Posted in the Facility

Financial Statement

Adequate TUR Options

Cost and Financial Analysis

Pareto Analysis for Prioritization of Opportunities

Quality Analysis

TURTeam Developed

Appropriate Personnel

Senior Management Support

Charter Established

Facilitator

-3 1-


C * Implementation of the Plan

1 .o Responsibilities

1.1 Performance Expectations Established

1.2 Time Frames Established

1.3 Annual ObjectivedGoals

1.4 Training Needs Established

2.0 Options

2.1 Engineering Support

2.2 Responsibilities Assigned

D Monitoring of the Plan

1 .o GoaldObjectives Review

1.1 Frequency for Reviews Established

1.2 Performance Expectations Reviewed for Adequacy

1.3 Option Reviews

1.4 Cost and Reduction Analysis

1.5 Quality Analysis

E TUR Planner Certification

1.0 Statement of Validity

1.1 Signed and Current

1.2 DEP Review

-32-


F TURADocument Review - J. Pointon

The following is a partial listing of documentation that may be available at the site that

willprovide information or cross checks to information within the TURAPlan.

OSHA Forms and Records:

b OSHA 200 - Accident and Injury Log

b Hazard Communication Standard Records

Written plan

Chemical Inventory

MSDS File

Employee Training Outline

b Lab Safety Standard

Chemical Hygiene Plan

MSDS File

b Respirator Program Requirements

b Industrial Hygiene Surveys

-33-


TURA Document Review, cont.

Federal and State Environmental:

Air Pollution Registration Forms

Material Profiles

Emissions Estimates

Water Pollution Control

NPDES Permits

Wastewater Discharge Permits

Sewer Connection Permit

Wastewater Monitoring Reports

Hazardous Waste Management

EPA Generator Registration (LQG, SQG)

Waste Profiles on File with Hauler

Hazardous Waste Manifests

Waste Storage Inspection Reports

Annual Waste Summary

RCRA Contingency Plan

UST Registrations (and above ground)

Spill Prevention and Control Plan

CERCLA Notification (Sec. 104)

SARA Notification (SEC. 302, 31 1)

SARA Reports (Tier and Form R)

-34-

CHEMICALAND POLYMER INDUSTRY MODULE ~ ~

TURA Document Review, cont.

Miscellaneous

b Fire Prevention Plan

b Emergency Response Plan

b Receiving Records

b Purchase Records

b Material Inventory Records

b Production Records

b Shipping Records

-35-

CHEMICAL AND POLYMERINDUSTRY MODULE

REFERENCES

Chemical Manufacturers Association

1.

2.

3.

4.

Resmnsible Care. 199 1 Progress ReDort , Washington D.C., 1991.

Molly Bloomfield, Chemistry an d the Livingban ism , New York, John Wileyand

Sons, Inc. 1977

Rene G. Gonzalez, Petrochemical Handbook 1991, in Hydrocarbon Processing,

March 1991, Vol70 No. 3, 1991

The Toxics Use Reduction Institute, Curriculum for Toxics Use Reduction

Planners , Second Edition, University of Massachusetts at Lowell, 1991.

-36-


SUPPLEMENTALREADINGS

-37-


A

B

C

D

E

F

G

H

I

J

K

L

SUPPLEMENTAL READINGS

"CMA's Responsible Care - Pollution Prevention Code of Practice"

"Design for Zero Releases", WF Early 11 and M.A. Edison

"Obstacles to Waste Reduction", Joel S. Hirschorn and Kirsten Oldenberg

"Pollution is Waste", J. Redman

"Voc Control or Elimination From Coating Operations", KJ Miller

"Source Reduction of Chlorinated Solvents: A Multimedia Approach", A.

Y azd an i

"Managing Hazardous Wastes Not Enough", J. Underwood

"The Tools of Quality" Part IV: Pareto Charts. Qua litv Proaress, November

1990, pp 59-61.

"Recycle Your Plastic Waste", W.C. Kohlke. Hvdrocarbon Processinq 1990.

"CMA Members Attack Waste", CMA News, March 1991.

"Strategies for Reducing Pollution at The Source Are Gaining Ground", Lois R.

Ember, News Focus C & EN, 1991

"Supercritical Carbon Dioxide in Chemical Processes", GA Leach, American

Institute of Chemical Engineers, Spring National Meeting, Houston, 4/7 -4/11,

Reprint, N.49E, November 4, 1991.

-38-

I'

POLLUTION PREVENTION CODE

Member Self-Evaluation

Due date for the completed form is August 31,1991.

Contents of This Report:

1. Instnrctions for the User

2. Serf-Eualuatbn Form for the 1990 Reporting Yew

3. A GREENPre-AddtesSed label is included for your convenience to send the completed Seg- Evaluation Form to:

Dr. Edward J. Heiden ~ e i d e n Associates, Inc. 2100 116 Street, N.W. Suite 300 Washington, D.C. 20037


-PORT 1: MEMBER SELF-EVALUATION FORM FOR THE 1990 REPORTING YEAR

instructions for the Company Responsible Care Coordinator:

1.

2.

3.

4.

5.

6.

7.

ThisformistobesubmittedannuallytoCMAbyeachmembercompany. m y e a r t h e due dateisAugust 31. 1991. Please submit dinxtly to:

Dr. Edward J. Heiden Heiden AssociateS, Inc. 2100 M Street. N.W. Suite 300 Washbgton, D.C. 20037

Indicate on page 1 the number of your member company's facilities that are subject to the Code. Each company's Responsible Care coordinator must report the implementation stage for all facilities subject ,to the Pollution Prevention Code on this form.

The Self Evaluation form for the 1990 reporting year only covers the 1- waste and release reduction management practices. mer the draft waste management practices are approved. CMAwlll include them in the SeXEvaluation F m for the next reporting year. The 199 1 reporttng year request will be sent In April/May 1992.1

For each Management Practice on the following pages. indicate the number of facilities that have attalned each fmplementatlon stage, Identify the current Implementation Stage for each of your faciUties at the time you complete the fonn.

For the Industxy 'I.end Data, show the total number offadwes in each appropriate box The total number of facilities for each type of Tnnd Data should equal the total number of facilities subject to the Code.

Only subject faditlcs owned or operated as of the reporting date should be included.

The Implementation states are!:

State1 - Noaction Stage XI - Evaluating company practices against Code practice Stage III - Stage N - Stage V - Code management practice in place Stage VI -

Developing action plan to implement Code practice Implementing action plan

Implementation reviewed and reaffirmed this year.


T-1. Release of Subs" as R-

and ported under SARASection 3 13:

T-2 Wastes generated, as d&ed and reported in CMA's annual waste survey.

Industry Trend Data

Report annually to CMA or I t s designated agent. the number of facilities for which a"iUa1 report to CMA has or has not been submitted:

F O m I Form R I N R

I I

Member Company Name:

Annual dpnual Report Not Report submitted. SUbdttCd* Total Facilities

- . *Enter the number of facilities. . . . . -*.,. ~ ._.._ ..- ~ .. NOTES:

1. CMA expects to receive release data only from those facilities that are required to complete the Fonn R following the requirements in the Supdund Amadmat and Reauthorkation Act (SARA) Section 313 and E€?A's clarifying regulations and instructions.

2. Instruction: Under Form R enter the number of fhcilitles that are submitting TRI data to CMA.

Line T-1:

P These faduties should submit the same data as EPA requires. The 313 Form R release data are due b EPAon July 1,1991 and to CMA on July 31.1991.

P W r Form NR enter the number of facilities that jue not s u b m to the EPA reporllng requirements. These fadities should complete Form NF& Companies, not requlred to report 3 13 release data to EPA may volunteer to send release data to CMA. These fadties are not required to submit TRI release data to CMA as an obligation of membership. ~

Line T-2

0 The 1990 Reporting year is the first year that facilities must complete CMA's annual Waste Survey as an obligation of membership under the Pollution Prevention Code.

-

2

, I .

. .

POLLUTION PREVENTION CODE OF MANAGEMENT' PRACTICES

REPORT 1: MEMBER SELF-EVALUATION FORM FOR THE 1990 REPORTING YEAR

Member Company

Name:

Responsible Care Coordinator

Name:

Address: -

Telephone: )

Number of facilities subject to the Pollution Prevention Code

, * .

. .

stages

10. An ongoing program for promotion and support of wast and release reduction by others, which may, for examplc include:

a

b.

C.

d.

e.

f.

Sharing of technical information and experience witl customers and suppliers:

Support of efforts to develop Improved waste an( release reduction techniques:

Assisting in establishment of regional airmonitoriq networks.

Participation in &orb to develop consensus ap proaches to the evaluation for environmental, health and safety impacts of releases:

Providing educational worbhops and training mate rials:

Assisting local gavemments and others in establish. ment of waste reduction programs beneMing t h e general public.

.. .,..-,.-

I N V

._ ..

-

VI

3

Management Practice 1: __

ORGANIZATIONAL COMMTTMENT __

A clear commitment by senior management throrrgh policy, conimunications and resources, to ongoing reductions, at each of the company’s facilities, in releases to the air, water and land and in the generation of wastes.

Possible Considerations:

o Commit cntirc organization through Corporate plicics, dircctivs, and communication to support your wastc and relcasc reduction practices.

o Idcntify and providc fesourccs.

o Intcgratc corporate goals into facility and dcpartmcntal goals, or vicc vcrsa.

o Assign program rcsponsibility at highcst appropriatc Icvcls.

o Assign corc mcmbcrs to program.

o Considcr company, facility, and cmploycc inccn tivcslrccogni tion.

Other:

Management Practice 2:

FACILITY INVENTORY

A quantitative inventory at each facifity of wastes generated and releases to the air, water and land, measured or estimated at the point of generation or release.


0

0

0

0

0

0

0

0

0

Usc cxisting information and data for your invcnlory.

Idcntify sourccs of multimcdia wastcs and rclca.scs.

Dcfinc all parametcrs n d c d to mcasurc progrcss (yardstick).

Idcntify additional needs.

Dcfinc your bascline,

Establish a rccordkccping and tracking systcm.

Periodically rcvicw data quality.

Dcvclop consistcnt mcasurcmcnt tcchniqucs.

Dcvclop and maintain cicar, mncisc dokumcntation of mcthods used.

Other: (handwrite in final)

Remcmber EPA--Waste Minimization Critcria strcsscs cost _--_ trac ki nnlalloca tion.

USC production data to normalizc the changcs in thc rclcasc data f I n d ex).


POTENTIAL IMPACTS Evaluation, sufficient to assist in establisliing reduction priorities, of the potential impact of releases on the environment and the healfli akd safety of employees and the public.


o Rcgulations

o Odors and visiblc rclcascs.

o Employcc and public scnsitivitics.

0: . Population distance and density.

o Voiumc and toxicity.

o Rclcasc pathways.

o Modelling and monitoring.

Other:


EDUCATION & DIALOGUE Education of, and dialogue with employees arid members of the public about the inventory, impact evaluation, risks to the community and waste and release reduction priorities.

Possiblc Considerations:

o Coordinatc with thc spokcspcrson(s) (intcmal and cxtcmal) for thc sitc/facility.

ldcatify and u.sc thc mcthods .sct up undcr thc Community Awarcncss and Outrcach Scctioa in thc Community Awarcncss and Emergcacy Rcsponsc (CAER) Code on Managcmcnt Practicc.

o

o Work with thc .spokcspcrson(s) to idcntify topics for cducational matcriak with thc spokcspcrson(s).

o Emblish a mcchankm to m i v c and act on cmploycc and pubUc rclating to thc wa..tc and rclcasc rcduction practicn fccd back.

Other: Provide technical hckm to tlw spokcspersonfs)


PRIORITIES AND PLANS Establishment of priorities, goals and plans €or waste and release reduction, taking into account both community concerns and the potential health and safety impacts as determined under Practices 3 and 4.


0

0

0

0

0

0

0

0

0

0

0

0

Other:

Identify rcsourccs and spcciali!ts nccdcd to assm facility P-0

Analp procnscs for d u c t i o n opportunitics.

Dcvclop altcmatives for sourcc reduction, rccyclc/rcusc, or trcatmcot of wastcs and rclcascs.

Intcgratc thc mults of thc potcntial impact asscssmcnt.

Intcgratc thc rcsultc of cmploycc and public conccms.

Scrcco altcrnativcs and idcntify potcntial barricrs.

Pcrform cconomic and oon-monomic bcncfit analysis of altemativcs.

Rank and sclcct altcmativcs.

Identify implcmcntation rcsourccs-

Dcvclop implcmcntation schcdulc.

Dcvclop and prcscnl rccommcndations to managcmcn t.

Incorporatc into budgct and planning cyclc. *


IMPLEMENTATION Ongoing reduction of wastes and releases, giving preference first to source reduction, second to recycle/reuse arid third to treatment. These techniques may be wed separately or in combination with one another.


0

0

0

0

0

0

0

0

Implcmcnt your rcduction plan in accordance with thc priorities cstablbhcd in Practicc 5.

Progrcss up thc rcduction hicrarchy ovcr timc.

Obtain rcsourccs. Consider outsidc rcsourccs,

lmplcmcnt procedural changcs.

Jmplcmcnt appropriatc cmploycc training programs.

Install cquipmcnt and/or mdiry proccsscs.

Maintain cmploycc support through recognition and awards programs.

lntcgratc with thc quality proms.

,

Other:


MEASURE PROGRESS Measurement of progress at each facility in reducing the generation of wastes and in redwing releases to the air, water and land, by updating the qtrantitgtive inventory at least anntialiy.


0

0

0

0

0

0

Updatc invcntory.

Evaluatc projcctcd versus actual pcrformancc of implcmcntcd altcma tives.

Use indexing, as appropriatc.

Maintain rccordkccping and tracking syslcm.

Pcriodically rcvicw data quality.

R c p r t progrcss to managcmcnt.

Other:

,/--


COMMUNICATION Ongoing dialogue with employees and members of the public regarding waste and release information, progress in achieving reductions and future plans. This dialogue should be at a personal, face-to-face level, where possible, and should emphasize listening to others and discussing their concerns and ideas.

Possible Considcra tions:

0

0

0

0

0

Coordinate with spokesperson(s) (internal and cxternal) for the sitelfacifity.

Use thc communication proccdurcs sct up undcr thc Community Awarcncss and outrcach Scction of thc CAER Cadc on Managcmcnt Practiccs.

Work with spokcspcmn(s) to periodically dcvclop mcssagcs on the company's progrcss to implcmcnt thc wastc and rclcasc rcduction actions.

Bccomc morc aware of thc nccds of your spkcspcmon(s). U.sc non-tcchnical languagc to dcvclap your mcsagcs targctcd at your aud icncc.

U.sc misting mcchanisms to act on fccdhack rclating to waslc and rclcasc rcduction activitics.

Other: (Handwritc in final)

Bc available to answer tcchnical questions and parlicipatc in all intemallextemal communications activities.


INTERNAL INTEGRATION Inclusion of waste and release prevention objectives in research, and in design of new or modified facilities, processes and products.


o Involvc cnginccring, rcscarch, purchasing, main tcnancc, and busincss groups.

Intcgratc reduction pMciplcs into busincss and strategic planning, product dcvelopmcnt, facility dcsign and modification.

o

o

o Appropriatcly allocatc costs.

o

Includc rc1ca.s~ d u c t i o n conccpts in ncw product. and product returns.

Include Wask and Rclcau: Rcduction as part of cnvironmcntal revicws/a.sscssmcnb.

o Considcr compliance constraints.

Other:

I . . ' /


INDUSTRY OUTREACH An ongoing program for promotion and support of waste and release reduction by others which may, for example, include:

a. Sharing of tcchnical information and cxpcricncc with customcrs, and suppiicrs (camcrs, and warchouscs, ctc).

b. Supporting cflorts of othcrs to develop improvcd wastc and relcasc rcduction techniques.

C. Assisting in thc cstablishmcnt of rcgional air monitoring networks.

d. Participating in cffortc to dcvclop consensus approachcs to the evaluation of cnvironmental, hcalth and sarcty impacts of relcascs.

e. Providing (and/or sponsoring) cducational workshops and - training matcrials.

f. Assisting local govcmmcnts and othcrs in cstablishmcnt of wastc rcduction programs bcncfitting thc gcncral public.

OTHER: Identify and impIement intcmal channes which will rtducc releases in the customcr/supplier chain.

support state CIC prop7ams.

for zero Using these principles, you can improve cost competitiveness, minimize liability and be a "good neighbor" in the community

W. F. Early II and M. A. Eidson, Stone & Webster Engineering Co., Houston

1)ESICJSI:;G ANY C:HEMICXL PROCESS for zero releases requires attention to the total design process, and not just a dependency upon the latest technological advances in equipment:

.4 comprehensive review of the process is needed Historical data and input from the operators of the pro-

Correct equipment selection is made A systematic hazard review of the system is performed

followed by proper instaliation and operation. I he uncontrolled release of hazardous liquids and gases

into the environment primarily can be divided into major or minor releases to help in the understanding of their source and control. Releases can be to the air, soil or water, each having the potential Ibr a serious personnel o r environmental impact. hla,jor releases are primarily from equipment tailiire, relief to prevent a more serious event. o r from human error. The origination of minor releases typically can be chsit'icd as eithcr from a fugitive sourcv o r a point source. Certainly. point source releases ha1.e thr potential of Iiecom- irig major releases.

Design criteria. To reduce the possiliility 01' minor re- leitses. the designer must concentrate on designing equip- iiic'iit and piping with the intent of being completely leak- prool' and tail-proof. Even the smallest component has the potential lor a relcasc and even the smallcst release should be ol'concern. Attention to detail via equipriient specification, installation and operation will aid in the reduction of minor i&~ases.

An over\%\ 01' the process and the facility. along with a : ) i ~ o ( x x hazard review will help i i i the prcvention o l niqjor I r l v a s r s . I b fitcilitate the overview, a frrsh virtvpoint is ol'tcn iic.c.essar); rcquiring designers not instrumental t o the rffort to supplement the review teani.

Process conditions, layout. The first step in examining id^ part of the design is a thorough review of the chemical process and its general philosophy. I f any part of' the process \vi11 allow for potential operation under lower pressures or .smperatures. then the potential behind releases in these ar-

15 can be reduced. The opportunity for high potential en- -9 rcleases should be minimized where possible.

Decreases in pressure directly decrease the potential for a iiiajor release. L'se of larger line sizes or placement of pres- wre reducing valves as far upstream as possible will minimize the length of high hazard potential lines and equip- iiient. However, there is often a direct cost increase which

cess are reviewed

-.

must be accepted, and this has not been commonly done. Consideration of minimizing line lengths should be re\.irwed in the plant layout by keeping high pressure systems relatively close together i f possible. Running a high pressure line great distances can be avoided if the pressure is to be reduced at the destination and other considerations such as two-phase flow are not limiting.

High temperatures increase the stress and corrosion of piping and equipment materials of construction. Therefore, reducing operating teiiiperatures as soon as practical \vi11 increase equipment longevity and decrease failures. For instance, heat exchangers may be located so as to maximize cool operating lines and equipment. An exchanger should not be placed so that several hundred feet of hot piping is required to reach it. Some savings may also be obtained from reduction in personnel protective insulation as well as improved service life.

History and experience. An important aspect in achieving a well-designed system is to get input from those most closely associated with the process itself. Primarily, this is the operators. From their hands-on experience with the same or similar processes, they are an excellent source of information upon which to base design features which minimize releases. Operators can also identify potential failures. Also, operator input on how plants currently operate can give you an idea if your new design might be successful because of its familiar- ity of approach o r whether it might be unduly complicated and foreign. Soliciting operator input not only produces valuable information, but also provides an opportunity for plant ~ ~ ' r s ~ i n n c l tu "buy-in" to the design.

Historical plant records are frequently difficult t o obtain. so operators are an invaluable for such data. For instance. the reproduction of operating conditions in a laboratory for corrosion tests is often unable to fully create true process conditions due to small or unrecognized critical compunds or factors. Success and failure stories based upon plant data and csperience arc then necessary for design success.

Harard evaluation. A new design often contains elements which can create rclritses simply because of the interrelation- ships and influences of vach component upon the other. For instance, a high I ' I ( J w or pressure created by one component can cause a downstream failure and produce a niajor cherni- cal release. To ensure that all precautions are considered. a process safety hazard review is becoming common. I t is typically performed as soon as the piping and instrumentation diagrmns (PIDs) are released lor detailed design.

A hazard and operability study (HAZOP) in accordance with AIChE Center for Chemical Process Salety (AIChE- CCPS) Guidelinesfor Hazard Evaluation Procedures has become a common tool and is even mandated by California statutes. API has now issued Recommended Practice 750 which includes process hazards review and the CMA has drafted similar proposed methods to ensure process safety. Additionally, OSHA is currently proposing regulations requiring a hazard review of the process for systems containing Specifically hazardous chemicals. OSHA's regulations also contain guide-

Hydrocarbon Processing, August 1990 d7

lines for performing a process safety hazard review. A process satkty hazard review can evaluate circumstances

before they happen. An analysis of the potential causes of fkilrire will reveal areas of possible frequent or catastrophic rclcascs. Systematically, all types of operating deviations are corisitlt*red for their potential to initiate a release.

Once the- areas of high release potential are identified. then specific precautions can be built in to those areas to reduce the likelihood of failure. For instance. redundant controls and indicators may be required, or relief valves may ha\.e to be resized based upon newly discovered cases, or the design pressure of a vessel may have to be upgraded. Equip- ment failure histories as well as release frequencies may be utilized to assist in the evaluation. Resources should be concentrated on those areas with the greatest potential for releases and in order to effectively mitigate thost, areas.

Design considerations. The most frequently discussed topics for minimization of releases are piping details and equipment application. Since they are also the most frequent sources of release, these types of releases iind their sources are addressed first.

Minor releases are typically classified as either "liigitivc" or "point source." In general terms, fugitivt. releases or emissions are typicallv small (usually undetecwtl) drips arid leaks which escape from packings. seals and connections. Sources of fugitive emissions are typically flanges. v a h ~ packing, \dves , relief valves and pump seals. Point source releases are typically considered to be larger antl more ob- servable releases generated from a single and easily identifi- able item. Point source leaks are more commonly from vessel failures from corrosion, overflowing eciuipriiciit, improper venting, and spills from sampling and loading. Point source releases also have the ability to become niajor releases.

Flanges and welded connections. Although flanged connections are ii necessity in rapid piping assenihly. equipment assembly and removal, flanges are ii high probiible source for leaks and fugitive emissions especidly near rotating (vibrating) equipment. The use of flanges can often be replaced with welded fittings if deemed pr;ictic;il. Placing flanges underground is totally unacceptable because of the ease of undetected releases and should be avoided. ,411 flanged connections should be kept above ground or placed in accessible locations so that they can be insprctecl. When flanges are necessary. procedures should be estahlished li)r correctly assembling and tightening the flanges, antl strict adherence to proper gasketing should be established.

Depending upon the service, a higher pressure classifica- tion piping (hence flanges) is often specified. For instance, hot oil circuits are typically specified for 300# AKSI minimum flange.

When welds are used, quality control should be main- tained over welding procedures and \vcltling supplies. .4 single compromise of the weld procedure or the use of a single wrong welding rod can jeopardize the integrity of the entire weld. Visual and nondestructive tests will usually not un- cover these flaws, but once in service the results can be serious equipment failure and eventually a release.

A common source of loss of integrity in both ~ e l d t d antl I'langed systems is improper supply of' materials from ware- housing. Proper management controls shoultl be. established to minimize this problem.

valve oper;ition should be reviewed as part of a process hazard review. V~iIve placement should also be reviewed in re- gard to venting or draining of hazardous materials. Use of double block v;il\.es or plugs can also stop potential leakage.

During dcsign. the types of valve packing, seals and gas- kets should be reviewed for opportunities to reduce leaks. Existing plants should be surveyed to identify those components that have proven reliable in service. Reviews of leak detection records will aid in determination of proven designs antl the causes lbr hilures of troublesome items. Valves known for long service lifk and leak resistance should be specified.

Relief valves. K e d y installed relief valves are usually tight and do not leak. but after a few months of service or if lifted just once. their reliability clrcreascs. I f relief valves ;ire discharged to the atmosphere, they may become a slow iintl

unexpected fugitive release source. Slow leaks into closed flare systems can also result in fugitive emissions if thc flare system does not effectively combust small quantities o f com- bustihles. Relief valve maintenance should therefore be SIX-

d i e d during design t o he an integral part of any zero relc;ise proyram, and spare parts should also be reviewed to anrici- pate pr0bkJii arcas. Equally as important is application 01' the appropriate relief valve design or materials o f construction. An improper choice will lead to leaks and undesired rcleases.

I n choosing the proper relief valve design. the siicccss ol' designs in existing service should be rcvirwctl. Each coiiipo-

nent of the v d v e should be strictly specified and reviewed ['or compatibility with its service. A single failure of only one o f the many coriiponents within a relief valve (e.g., "0" ring or gasket) is all that is necessary to cause a release.

Pumps. Scvcral pump designs and features are devoted t o niinimizing Iviiks. h'hether double seals or magnetic drive se.allcss or c;in-type sealless pumps are used, these tlrsigns iire rapidly hccorning more common in every kind of scr- vice. Many articles can be found discussing thc benefits i d

limitations of' thew katures. Utilizing these atlvances are certainly iitIv;int;igeous in eliminating fugitive releases i f properlv applied.

Transfer lineslhoses. When considerinq transliar lines ;ind hoses. t\vo iireiis need to be revie\ced: 1 . Use i i t t i r right hosts and 2. 1,ayout. A hose is an inexpensive piece 01 q u i p - Iiicnr when compared to other operating elements. I)t.sign- ing hoses for only material compatibility is not sull'icierit. ho\vever. Too often. hoses are not specified to handle the rig- ors of constant abuse from handling. Wear and tear on hoses niust be considered in layout with an eye toward minimal physical abuse 01' the hose since hose failures arc a commion source of release.

Loading antl transfer lines require attention to their physical location i i i i.tl;itionstiip to the. supply systeiiih ;iritl equip- mcnt they iritci.connect. Low points left in the line after transfer can f'requently cause small releases. Revie\vs of the entire piping s!.stem for operability, for drainage ant1 effi- cicrit purging prior to disconnects are required t o C I ~ S U I ' ~ that e\wi the smallest of' releases can be eliniiiiatecl.

Installation. Designing for zero releases does not wIIi tvitti

thc t'inal issue o f the drawings or quiprnerit spc,cil'icatioris. Prior t o startup. a review of the installation is nppropiiit? 10

make sure tha t i t conlorriis to the final design. I,(I*I i i i i i i r i r c

c.li;~iii~es may ti;i\.c comproinisecl thc oriqiii; i l intcrir 1 0 i i i i i i i -

i i l i / t , I . I . I ~ * ; I \ G , , 0 l r c . r i rt.ft.i.1.(.(1 1 0 t ) \ ()SH \ .iii(I i i i i ! j ik i i ' \ , I \ ;I

The authors William E ("Skip") Early I1 is a manager of safety and risk management in Ihe Process Technologies and Project Services Division. Stone B Webster Engineering Corp.. Houston. He has a broad process background covering many HPI designs. He holds an MS degree in chemical engineering from the University of Mississippi. Mr. Early is active in LChE's Safety and Health Division. serves on an AIChE-CCPS sub-

mmittee and is a member of SRA and ASSE. He is a registered engi- -er in Texas.

' lark A. Eidson is a senior engineer in the Safety and Risk Manage- ent Division, Stone 8 Webster Engineering Corp., Houston. His back-

ground is in process design, environmental regulations and safety is- Sues. He holds a BS degree in chemical engineering from Texas A&M University and is a registered professional engineer in Texas.

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Circle 87 49

i

The Obstacles to Waste Reduction

Both industvy and public-interest groups remain attached to the established methods of pollution control. Until we come to undustand

why, the long-term benefits of waste reduction will remain elusive.

Joel S. Hirschhorn and Kirsten U. Oldenburg, Office of Technology Assessment, Washington, DC 20510

azardous waste reduction-reducing the generation of all environmental pollutants by changing indus- H trial production processes, technologies, proce-

dures, raw materials, and sometimes products-is gaining popularity. Congress has shown considerable interest in waste reduction, and the Environmental Protection Agency (EPA) has a new Office of Pollution Prevention. The EPAs Science Advisory Board stated that pollution prevention should be a major strategic initiative for the agency and companies are discussing waste reduction more often. But this new interest by industry and government in what is an old idea may not be as significant as it seems, and a national, long-term commitment to waste reduction as a serious complement to traditional environmental protection is not assured.

While fewer companies and environmental groups are ignoring waste reduction, many people and organizations give it a low priority relative to other environmental issues, to regulatory problems, and to traditional forms of waste management. Waste reduction seems different than other areas of federal involvement. Because its benefits appear so great

AS. Hirdhora ir a sen&r 451oe1(te at the Gmgressibnal Office of T e c h n d ~ Assessment @Z& who has diraftred studies on hazardous coartes that h e w shape the 1981 a m a h e n t s to the Resource Con- seroation and R ~ O W M Act, the 1986 Superfund Amendment and Reauthorization Act, and rr#rcll d e duct ion biik The author o f more than 100 prrpers and rr#rcll books, he holds trw US. patents and is a frequent maker on hazardous waste at conferences and workshop Prior to joining OTA, he (1k~1 a pmfesor of engineering at the Unin. of wlrcarcin at Maahn. K.U. Oldenburg, a pol& anal@ with OTA tbr the past five gears, current& conducts msearch on the Superfund proqnm, and munid pal wlid waste. The author or ewu*cor of numerous artides on d e duct ion and stmtegic materiak, she was assistant prolecr director of the 1986 OTA report, "Serious Reduction of Hazardous WaCe, and a special w t , " h n n twIurion to Prowntion: A l h g - lpss Report on Waste Rodrrction" (1987). She earned her BS degree in materid science and engineering h m the Unio. o f crrliomia at Berkefq.

.-_

and widespread, it seems as though it should happen by itself. Because it is easy to miss the obstacles to waste reduction and to overlook the negative consequences of relying on industry and the states to implement waste reduction, not understanding the importance of federal waste reduction policy is also easy.

The public has heard little about waste reduction, partly because waste reduction as good news does not compete well with all the bad environmental news. They have not linked past successful energy conservation and preventive health care experiences to the possibility of future environmental waste reduction. There is little public debate on federal waste reduction policy, programs, or appropriations.

Moreover, widespread frustration with the ineffectiveness and inefficiency of the current pollution control system has not created a viable, parallel preuention strategy that is attractive to government, business, and environmentalists.

After a hard analytical look at the facts, many people agree that a major national shift away from traditional regulated end-of-pipe pollution control to voluntary pollution prevention is technically and economically feasible, but it has not yet occurred. Extensive data from industrial examples make the case that true waste reduction, as a preventive tactic, provides the most certain environmental protection and is profitable to industry. Pollutants not produced cannot harm humans and the environment. Waste reduction can cut industry's escalating waste management, pollution control, regulatory compliance, and liability costs, and it can do so with small investments that yield returns within weeks, months, or rarely, a year or two-at least in the initial stages.

If we accept these findings, then we must understand why more industry and public-interest groups do not aggressively support government help to industry, help that is designed to reap the environmental and economic benefits of waste reduction. Some believe that a major federal effort is

June 1989 31

unnecessary because industry and individual states are doing enough. There are more and more publications and conferences about waste reduction, and some states have passed laws and set up programs to help industry reduce waste. But these efforts are very small compared to established environmental programs, are often focused on minimizing use of landfills disposal rather than on true waste reduction. and frequently directed to small waste generators who account for only a fraction of the nation's environmental waste generation.

\Ve believe that many in the private sector have not yet seen the critical need for a major federal waste reduction program because they are worried about possible secondary impacts. Industry fears burdensome waste reduction regulations. Companies in the waste management and pollution control business may lose markets, and environmental organizations worry about losing support for established regulatory programs. These concerns, i f not confronted. will handicap public debate and impede the development of federal waste reduction policy and well-funded programs.

The real problem The new interest in waste reduction may hide a serious

national problem: nearly every part of American society is mentally locked into the established, institutionalized pollution control culture, a paradigm that defines environmental protection in terms of what is done to wastes and pollutants oncc they are produced. Many people do not realize that pollution control often transfers pollution from one regulated environmental medium to another, and sometimes the other medium is a less- or nonregulated medium. And pollution control is based on the concept of safe or allowable levels of pollution, which, because they are so difficult to set. means that many hazardous substances remain unregulated while debate continues for years. Pollution control also pits economic and health benefits against one another.

Another problem. particularly in the environmental and public-interest community, is the difficulty in seeing waste reduction as a fundamentally different strategy to achieve commonly accepted environmental protection goals. The switch from pollution control to pollution prevention is a classic esample of a paradigm change-a truly profound change in the way people think about something. Changing to a new paradigm takes time. In the interim, most people fail to see the comparative advantages of the new paradigm and the old one continues to prevail. And so it is for waste reduction. .4lthough many do not see waste reduction nega- tively. they do not see it as better than pollution control.

These problems help to explain why stepping briskly from belief in waste reduction to political action appears to be impeded by ditfuse and cautious support for (rather than esplicit objection to) waste reduction as well as (at times) by subtle attempts to redirect waste reduction policies and pro- firams. particularly in favor of recycling and waste treatment.

A number of waste reduction bills have been introduced in Congress to greatly espand the federal waste rtcluction

Loading and unloading facilities at Eastman Chemical Products. .4' pipelines, tanks and pumps at site are restricted to one product un all lines halve filter systems. Photo courtesy of Eastman Chemic1 Products.

effort at the Environmental Protection Agency. to provide i consistent national framework (including how to define ant measure waste reduction). and to fund state programs While differing in a number of details. only one of thesc bills calls for traditional prescriptive regulations for in. dustry. Instead. the hills focus on government-provideL technical assistance to industry of a kind already proven ir several demonstration programs (e.g.. Ventura County, Cal. ifornia, and North Carolina). Last fall. the House and Sen. ate passed waste reduction bills but did not have time tc reconcile them in conference. Serious congressional consid. eration of waste reduction or pollution prevention in 1985 seems assured.

Although there are many dedicated people working to put waste reduction on the national agenda. there has heen l i t - tle widespread public support of such bills by either industry or public-interest groups. At a congressional hearing in April 1988, only one of several industry representatives supported legislation. The lack of visible. organized support appears to be inconsistent with the generally accepted benefits of waste reduction. Meanwhile. using the appropriations route. Congress has supported waste reduction b!- providing greatly increased funding for waste reduction in recent EP.4 budgets. but these funds still are only a tiny fraction of the EPA's total budget.

ing the technical and economic feasibility. costs. :in11 benefits of waste reduction is voluminous. Thus, there is no need to repeat yet again esamples of successful waste reduction. There is only need to caution that, just as zero risk and zero emissions make little sense, zero waste generstiorl for all industry is also an ahstrsstion that must yield to t l w I w s ~ t '

The problem of implementation. The literature detail--

A major national shift away from traditional, regulated, end- ,,f-pipe control to voluntary pollution prevention is technically and

??

economically feasible.

physics and chemistry. But the waste reduction literature does clearly indicate that it is sometimes possible to totally eliminate a specific wastestream. even a very large one. from a mature industrial process. Additionally. the level of yet unrealized waste reduction is large: the Office of Technol- ~)gy Assessment estimates that neither technology nor economics prevents industry from reducing its environmental wastes by up to 50% within the nest few years. Several industrial firms and federal agencies have adopted this level of waste reduction as a short-term goal. Research and development efforts could. in time. lead to even greater reductions.

The larger prohlem with implementing waste reduction in industry is that a host of nontechnical factors work against its application. One. for example. is lack of information: it is common for people in industry to conclude that they have exhausted their waste reduction opportunities when. in fact. they have not. Other factors are competing production priorities, the belief that legally required pollution control is Tood enough, lack of management support to allocate peo- ,e’s time and capital for waste reduction, lack of rewards

for successful waste reduction. accounting systems that do not allocate total environmental costs to production profit centers, incomplete data on the exact sources and amounts of environmental wastes. and the difficulty of simultane- ously spending resources on regulatory compliance and waste reduction. ‘4s a number of pioneering companies have shown, all of these, except the last, will yield to determined management attack from the top.

Some companies and states have adopted a hierarchy of waste management options with waste reduction at the top. To agree in principle with the primacy of waste reduction, however. is not the same as implementing it with a vigorous long-term commitment. For example, in 1976 the EPA adopted such a hierarchy for solid waste, but until waste reduction was publicly resurrected a decade later, it had devoted nearly no resources to its implementation.

Congress has made the critical leap in thinking. The Haz- ardous and Solid Waste Amendments Act of 1984 (HSWA) states: “The Congress hereby declares it to be the national policy of the United States that. wherever feasible, the generation of hazardous waste is to be reduced or eliminated as expeditiously as possible. Waste nevertheless generated should be treated. stored. or disposed of so as to minimize the present and future threat to human health and the en- 4ronment.” While Congress has unambiguously stated the

primacy of waste reduction. it has not applied the principle to all wastes and pollutants because HSWA deals only with legally defined hazardous wastes, a subset of all environmental pollutants. [The law also included minor regulatory requirements. Companies must certifv that they are pursu-

97 ing waste minimization. a term broadly interpreted by industry (and, until recently, the EPA) to include waste reduction, waste recycling, and waste treatment.]

Are current efforts enough? The most obvious explanation for the lack of interest in

establishing a major federal waste reduction effort is the belief that, for the most part, industry has gotten the waste reduction message. taken its primacy seriously, understands its benefits, and made the necessary commitments to implement it over the long term.

This hypothesis is not easy to affirm or deny. Because we have a dominant end-of-the-pipe pollution control system, we have very little systematic, reliable data on waste reduction, and we probably will not have data for some time. Based on the monitoring of waste reduction data from industry and government and participation at waste reduction conferences nationwide, the authors believe that much of the talk about waste reduction is misleading. We do not think that the nation has turned the corner on waste reduction implementation. Waste reduction has not yet taken hold as a key environmental protection strategy in government or industry.

Very few companies provide detailed information on their waste reduction performance on a plant or company basis. They speak in generalities or give specific examples that tell very little about the company’s generation of waste relative to changes in its production output. Much of the available data is misleading. Improving industrial efficiency by cutting waste production is variously called waste reduction, source reduction, pollution prevention, or waste minimization. There are no standard definitions. Companies often claim that activities (such as incineration) that follou* the generation of a waste, rather than only those that altoid waste creation, handling, movement, and management. art: waste reduction. Survey results and published papers show that probably 75% of companies use a definition of waste reduction that includes improved waste management and pollution control.

Data from government sources are difficult to interpret because wastes are accounted for by environmental media (which differ). It is also not possible to separate out waste reduction effects from effects caused by other factors, such as changing regulatory definitions, plant closings, and varying levels of regulatory enforcement.

Finally, companies may only pursue short-term waste reduction benefits. Waste reduction in any plant proceeds through several stages. Companies without long-term commitments to waste reduction often only tackle the first, easy, and low-cost waste reduction opportunities and then lose interest. They do not push waste reduction to its limits. As

33

waste reduction paybacks decrease and projects become more complex and dependent on capital and R&D, public policy will have to play a more critical role.

A few companies are providing good data showing that large amounts of profitable waste reduction can be accomplished quickly, But these companies are the exception, not the rule. Their successes do not mean that current public policy is sufficient: it only means that some companies have the resources to recognize the advantages and act accord- ingly. 3M's "Pollution Prevention Pays" and Dow Chemi- cal's "Waste Reduction Always Pays'' are more than slo- gans: they are simple statements of economic fact. These companies and others continue to work to overcome obstacles to waste reduction. Not every company will do so.

Competing industrial priorities Government intervention in the area of waste reduction

would create economic winners and losers, which may explain the general reluctance of industry to support a government program.

The steadily increasing national spending on the environment-now over $80 billion annually-helps companies understand the benefits of waste reduction. It also defines a business opportunity for many of America's largest manufacturing companies. Waste management and pollution control is not a niche market. More and more companies have been entering this business, often using the waste treatment expertise they gained internally. This is particularly true since Congress mandated the shift away from land disposal of hazardous waste.

When a company has a successful waste reduction program and is in the waste management business, it is difficult for it to see any advantage in supporting a government program that would assist other companies in reducing their waste generation, which would shrink the waste managementlpollution control market. A government waste reduction program would create some new consulting business, but there would be little demand for expensive hardware or engineering services.

When a company with a successful waste reduction program is not in the waste managementlpollution control business, a government program could reduce its competitive advantage relative to firms without a successful waste reduction program. Moreover, a company that has done it on its own may feel that it is unfair for the government to assist other companies with less initiative.

And what about companies without successful waste reduction programs? A company that has not recognized the economic benefits of waste reduction is unlikely to see much purpose in a government waste reduction program.

For all companies, and particularly for those without a successful waste reduction program and no waste managementlpollution control business, there is the understand- able fear that any federal waste reduction initiative, even if it is nonregulatory today, will lead to a traditional regulatory program tomorrow. Waste reduction, in other words. falls victim to industry's mistrust of any regulatory agency. (This is why some states have kept their waste reduction programs out of their environmental regulatory agencies.)

" I . , - b

Indeed, congressional waste reduction action in the context of the Resource Conservation and Recovery Act regulatory program for hazardous waste would support industry concerns. Few companies yet understand how a nonregulatory waste reduction program could make the regulatory programs easier to bear: most give greater weight to their fears of waste reduction turning into a regulatory program.

Industry has two major concerns about waste reduction regulation. One is that regulations requiring certain levels of waste reduction might result in the elimination of certain products and that the waste reduction concept might be es- tended to unregulated and postconsumer wastes. The latter is particularly threatening because, from the industrial perspective, a company that is not generating a harmful waste. or that is managing a waste in compliance with regulations. could be forced to change or drop an established. profitable product because of waste created late in the product's life cycle. Indeed, a new interest in municipal solid waste reduction (ordinary garbage and trash) is upon us.

The other is that a company voluntarily reducing its waste generation today-or yesterday-might be required to meet some arbitrary additional level of waste reduction at great cost and difficulty tomorrow. (This concern explains why some major companies may not be revealing past waste reduction accomplishments; they are "banking" them in case they are needed to satisfy future regulatory requirements.)

Public-interest groups: Priorities and skepticism

People active in waste reduction during the past decade are perplexed by the fact that so few environmentalists (and even fewer environmental and public-interest organizations) have made waste reduction a high priority. A few grass-roots activist groups have, but they do not concentrate on federal policy. The early writings of environmentalists, such as Rachel Carson, contain the prevention theme, such as avoiding the use of certain pesticides.

Early on, environmentalists accepted the pollution control strategy as expedient. Limiting. not eliminating, pollution wus a practical first approach to sol\*ing the newly perceived and overwhelming problem. Organized environmental interests and public policy, however. have become attached to the pollution control strategy. Environmental- ists, like everyone else in the environmental regulatory arena, have learned to play, maintain, and expand the mostly legalistic game according to established rules.

Expertise, priorities, and commitments are established. Partial wins seem preferable to gambling on a new strategy. Support of a federal waste reduction initiative might detract from political interest in and, possibly, funding for existing regulatory programs. Waste reduction might even make the limitations and faults of hard-won regulations more visible. Moreover, there is a deep suspicion among environmentalists that a nonregulafory waste reduction program might create oppoprtunities for industry to compromise rcgulatory programs without really eliminating pollution. Some cn i i- ronmentalists and people in government advocate the indi- rect approach of expanding end-of-pipe regulatory programs and improving enforcement, thus increasing costs to inclus-

There has been little w idwead public support for waste w reduction bills by either industry or pub Iic-inter&t groups.

try, which will then turn to waste reduction to lower costs. But this strategy discounts industrial responses to rising regulatory costs other than waste reduction. These responses indude plant relocation and closings, using traditional pollution control technologies, litigation, lobbying to change laws and regulations, and, sometimes, even illegal waste disposal.

Shared concerns. There may be mutally reinforcing silence on federal waste reduction policy. Simply put, private sector players (and even some regulatory bureaucrats) may have independently reached a similar conclusion: helping to create a federal waste reduction program might crystallize the uncertain secondary impacts-which are beyond their control.

Giving visible support to waste reduction legislation might lead to a snowball effect if others, particularly those who do not perceive negative consequences, join in. Silence seems safe, especially as long as the concerned parties believe that Congress will not pass major waste reduction legislation. From their perspective, this is a rational strategy because waste reduction is environmental legislation and, therefore, must compete for congressional attention with older, more established environmental laws that have active constituen- cies in government and the private sector. And the absence of good data can be used either to defend the position that a federal program is unnecessary or to delay action, possibly for years, while information is obtained. We see little chance of getting good data on true waste reduction for all of American industry for some years.

Addressing concerns about secondary impacts. Waste reduction supporters can adopt a strategy to broaden public support. First, they must make three assumptions: 1) the nation has not yet turned the comer on successful long-term waste reduction and is not likely to do so under current public policy, 2) the lack of private sector support results from the perceived negative secondary impacts of a federal program, and 3) overall, serious, long-term waste reduction is good for society as a whole.

Waste reduction proponents could tackle the concerns described earlier head on. For example, they might convinc- ingly argue that promoting waste reduction through traditional regulatory measures is technically infeasible and ad- ministratively impractical because of the enormous number and diversity of waste-generating situations. Waste reduction supporters can be unequivocally positive that, instead, technical assistance can and will work. Industry’s concerns are valid. In its report to Congress on the subject the EPA stated it is still studying the possibility of future regulation. Nor can current waste reduction bills rule out future regulation; some legislative proposals already contain a regulatory approach.

73 Waste reduction’s implied negative effect on the waste

managementlpollution control market can be countered by pointing to the large toxic waste site cleanup market and emphasizing that we can never reach the zero waste level- some waste will always be generated.

Concerns of environmental groups could be allayed by a commitment to maintaining the regulatory program, which, indeed, is necessary but not sufficient for a successful waste reduction program. A case might be made for increasing regulatory penalties and liabilities over time as industry becomes able to reduce its waste generation and exiting, in part, from the regulatory system.

More efforts to educate the general public about waste reduction and its primacy over pollution control would also help environmental organizations to rethink their priorities. The public benefits of waste reduction likely will offset the negative consequences and costs of not reducing waste. For example, if we could avoid the creation of 10 cleanup sites a year with technically and economically feasible waste r e duction, then we might avoid adding $100 million to the long-term national cleanup bill each year. Or, if industry cut 10% of its waste generation each year, which is now at over 500 million tonslyr. (1 billion MClyr.), then waste management costs of several hundred million dollars would be avoided. In comparison, the costs of state and federal technical assistance programs for waste reduction are not likely to exceed $10 to $20 million a year. Increased tax income on the additional profits that result from waste reduction savings could pay for such government activity.

In conclusion As always, we must learn from the past. The benefits of

waste reduction were recognized in theory over 10 years ago, but practice has not followed theory. Federal environmental policy has been part of the problem. And, even with new, strong congressional interest in waste reduction and much more attention to it at the EPA, progress may be slow until we understand why people and organizations cling to the old approach to environmental protection. Clearly, we are on the right path. Recently, President Bush noted that, “Reducing waste at the source is the best way to deal with the problem” of a rising tide of garbage and industrial waste.” The EPA and its new administrator have a unique historic opportunity to turn these words into reality. H

Recommended reading “Serious Reduction of Hazardous Waste,” Office of Technology Assess- ment, Washington, DC (1986). “From Pollution to Prevention,” OffKe of Technology Assessment, Wash- ington, DC (1987). Himhhorn, J. S., “Cutting Production of Hazardous Waste,” Technol. Rev. (Apr. 1988).

June 1989 35

is waste Being "green" is not only a very necessary public posture for the chemical industry today, it can also be very profitable if some aspects of being "green" are tackled with the right approach. Chemical engineers should be leading the way here. John Redman explains.

Public concern about the environment is nothing new. The Alkali Act of 1863 is evidence of that. In ringing tones Theodore Roosevelt, in his message to Congress in 3ecember 1907, said, "To waste and to destroy our natural resources, instead of increasing their usefulness, will undermine the very prosperity which we are obligated to hand down to our children, amplified and developed."

Do you remember the furore Rachael Carson's book Silent Spring caused in 1962 when it was published? The book warned of the dangers of DDT and other pesticides to the environment. It is a measure of the change in puMic perception that similar books today are considered fairly mainstream and cause little stir.

This change in public perception is part of a wider view on how man and his activities should interact with his environment. It affects what the chemical industry manufactures, what the industry intends to manufacture and how the industry disposes of the by-products of its activities. The gist of this article is to suggest that this view will go deeper and for the chemical industry to retain the initiative and try and stay ahead of public opinion the chemical industry has to look hard at the by-products it is producing, ask "Is it necessary to produce them in the first place'?" and then ask "Is throwing them away the best means of disposal'?". It is in answering these two questions that the chemical engineer has a very vital and essential role to play.

Cleaner technologies The main thrust of this new drive is what is known in "green" jargon as "clean or "cleaner technologies". It means, in plain speaking, waste minimisation. The idea is that instead of devoting your attentions to treatment of anything and everything that comes out of the end of the waste-pipe, you should be focussing on cutting down on what is put into the front end of the waste-pipe in the first place, and making sure what is put in is more benign, that is, less toxic, than what might have been put in. This approach also applies to emissions to air and solid waste.

What is fascinating, if not striking, about this approach to pollution control is that in very many cases it makes sound economic sense-it saves money compared to the present industrial norm. In some cases paybacks can be as short as a few weeks or months.

3M's Pollution Prevention Pays Before you get all huffy at this implied suggestion that you are less than careful in your design, construction and operation of process plant, and careless with your employer's profits, think on this The United States company 3M instituted a 3P (Pollution Prevention Pays) programme in 1975 By March 1988 it had made first-year only, cumulative savings of $420million That is, counting only what it saved in the first year of operation of some 2261 projects (663 in the United

Y -- TOXC waste in the USA (Photo: M Melford, Colosfic!) -

States and 1598 for inteclational operations) started since 1975. the company has saved a whole bunch of money which is significant compared -3 annual earnings after tax Annually in the United States the2 projects prevent 110.260 tons of pollutants being emittec to the air, 13,450 tons of pollutants being discharged to rive's or the sea, 1 billion gallons of wastewater and 303,OO: tons of sludge and solid waste having to be disposed c; In the company's figures on pollutants for its internalonal operations in 1987 it didn t have

1

If you have any doubts as to which is the answer, it appear! that 3M is saving more each year in first-year savings on pollution prevention projects. The cumulative first-year savings figure I have for two years previously, 1986, is something over $300m. I would suggest that as managers and workers are finding that the new attitude works, produces positive results and they are acknowledged and rewarded for it, they are tackling the problem with renewed vigour and enthusiasm.

(Photo. A Reininger, Colorifid)

to get rid of are 10,812 tons of air pollutants, 1,100 tons of water pollutants, 602m gallons of wastewater and 11,000 tons

3P+ Last year 3M launched a new, short-term phase.of its 3P programme called 3P+ (Pollution Prevention Plus). This is a $150m, five-year programme aimed at reducing 3M's annual hydrocarbon air emissions by more than 55,000 tons worIdwide--45,000 tons in the United States-aver and above other reductions achieved through its 3P programme.

3M is zeroing in on hydrocarbons because of the role they play in the formation of ozone, the most pervasive of the majo air pollutants near ground level (see E€, Mar 1989 p35). The priority for the company is to start in geographical areas where emissions from car exhausts and industry mean that the area does not meet ozone air quality standards.

It should be noted that 3M facilities do comply with environmental regulations but management has chosen to go for further significant reductions in air emissions through this programme. By mid-1992 3M will have eliminated or controlled at least 85% of its US air emissions, and by mh' 1993 it will have done the same for more than 80% of emissions in its international operations. To do this it is installing new control equipment at all existing fadilities that emit 100 tons or more of hydrocarbons per year, will install the best available equipment at all new sources that will emit 40 tons or more per year and will revise existing control plans so that individual source controls meet the new 3P+ standards.

continue to seek further reductions through its 3P program. The company's stated goal is zero pollution.

When all this has been completed the company will

Solvent recovery at Hilden If you are wondering how 3M has been achieving its waste minimisation, the company issues a bulletin called ldeas which-with headlines seemingly by a refugee from the show biz newspaper Variep-gives case studies. Under the headline "Tank laved, solvent saved, toil shaved" one bulletin explains how 110 tons of tank cjeaning solvent were being lost each year at 3M's plant in Hilden, West Germany. The plant had no solvent recovery capability so used solvent was processed by an outside contractor from whom 3M then bought the recovered solvent. Added lo the problem was excessive manpower requirements for cleaning the two 300 jallon vessels.

The vessels were in a batch process, and cleaning was iecessary to avoid contamination of the following batch when he colour of a coating solution was changed. Tanks were lushed with solvents and roughly cleaned by agitation of the ;olvents with the vessel's mixing propeller. It was then nanually cleaned with brushes, with an employee often being equired to enter the tank. Tank cleaning took around 3 hours,

1 or around 800 hours for the two tanks per year What they did at Hilden was come up with a fully

wtomated cleaning system which pumps solvent under high xessure through a rotating spray head. The old mixing tanks Nere replaced by specially designed stainless steel ones. The system incorporates sedimentation tanks to recover solvent.

The system cost $69,000. However, in its first year it saved 861,500 in solvent and labour costs because cleaning time Nas reduced from 3 hours to 10-20 minutes and operator time Nas only 5 minutes to insert the head. The system cleans nore thoroughly than the manual system. Reduced downtime ias increased productivity, and it has improved employee safety as the operator does not have to enter the tank.

More solvent recovery Consider another case under the equally excruciating headline "Film unit develops pollution solution". In a plant in Columbia. Missouri. 3M photographically prints electronic circuitry on to flexible copper sheeting. A developer solvent is sprayed on and the metal then goes through a water rinse. In the past the wastewater had then been discharged directly to the sewer. Analysis showed the water contained solvent.

To recover the solvent and ensure plant effluent continued its compliance with sewer regulations, wastewater was routed through a stainless steel decanter. During a short holding time heavier-than-water solvent settled out and was then distilled and recycled into the development process.

The cost of the system was $4000. including installation. Savings on solvent were $3100 in the first year and $20,400 over a four year period. More important, by cutting the amount of solvent, effluent discharge was kept within limits which allow a substantial expenditure on a wastewater treatment plant to be deferred.

,ste from neglect (Photo' M Melford. Colorifrc!)

k 0 g ISSUE The roots of 3M's 3P 3M's 3P programme arose out of the environmental 3wareness of the 1970s in the United States. Federal and state environmental laws emerged restricting pollution .eleases and tightening requirements for monitoring. The :onventional response by most of industry was add-ons at the 2nd of process waste streams. Accepting that 3M had to :omply, the then chairman and chief executive officer 3aymond Herzog recognised the costs of these add-ons and Nondered whether there wasn't another way to comply and {et keep products competitive by holding down these end-of- ine costs. From this emerged the 3P prog:amme.

3M states that the programme seeks polution reduction or xevention through: D product reformulation, development of non-polluting or ess-polluting products or processes by using different raw naterials or feedstocks; D process modification, changing manuficturing processes :o control byproduct formation or to incorwrate non-polluting 3r less-polluting raw materials or feedstocks; B equipment redesign, modifying equiprrent to perform Detter under specific operating conditions or to make use of svailable resources (such as by-products tom another xocess); and D resource recovery. recycling by-producs (for sale or for Jse in other 3M products or processes).

None of these concepts are new. What 15 new is the sompany commitment that has been put &hind it. The chairman is behind the scheme and there is a vice president 3n the board, Roben Bringer, who is respmsible for it. His title is Staff Vice President, Environmental Engiceering and Pollution Control.

Many of you, I am sure, at this point are saying, "Yeah, well 3M is yelling from the roof tops what we have been doing everyday." Are you sure of that?

Waste reduction at Du Pont Look at Du Pont. Fifty years ago, back in 1338, Lammot du Pont, the then president. recommended to h e Executive Committee that a proposal for the company to undertake a comprehensive study of stream pollution b referred to the Engineering Department for careful study. Less than a week later the Executive Committee acted on t k recommendation raising Du Pont's concern for waste to the Same status as that for safety and fire protection-and you know that no one can touch Du Pont on the excellence of its safeiy record. In 1980 Du Pont declared that it intended to minimis the generation of waste to the extent that is technically anc economically feasible. Recently it has instituted its ReSolace (standing for Source Reduction) programme. The compwy's Finishes and Fabricated Products Department came up with a 4Rs (Reduce, Reuse, Recycle, Recovery) general blueprint for waste reduction.

Despite its continuing policy over the ye&% Du Pont still believes there are real savings to be made. It has set itself the goal of reducing waste by 5% (Ib of waste per Ib of product) per annum with a 35% reduction by 1990 ampared with a base year of 1982.

:, which has had a waste minimisation policy of prime ;Ice for 50 years, going to achieve that? The answers an , Some are amazingly simple.

And how, you may ask, is F

Washdown savings Training first-line su=rvisors and operators a paper published a year aga says, has yielded larp reductions in the generation of was!e at several site. It giEs a typical example. Operators 5ave been told to "kee; the area clean" The reaction had b e - , to wash the area do.iln on a shift-to-

shift or day-to-day basis, without knowing that the wash was generating a hazardous waste. With fewer washdowns and greater efforts to avoid the need for washdowns, things have changed for the better. This initiative could be done quickly, required no capital investment and I suspect did a lot for shop-floor morale as operators realised they were being listened to and action was being taken on their advice.

Squeezing waste Another example from Du Pont. At its petrochemical plant in Sabine, Texas, the weight of waste from slurry and sludges has been about halved by squeezing excess water with a belt filter press. In 1984 the plant disposed of 16,500 tons of waste off-site. The next year the figure was 8035 tons. Landfill waste went from 12,500 tons in 1984 to 4910 tons in 1985. When you are paying for waste disposal and landfill by the ton, squeezing water out of waste can save you a lot of dollars.

1984’s RCRA amendment 3M is not alone in high-profile, pollution-cutting programmes. Dow Chemicals-awarded last year Chemical Company of the Year by Mike Hyde of Chemical lnsight for the second time-has WRAP (Waste Reduction Always Pays). Du Pont. with its Resource. and others are more low-key. What has concentrated the mind wonderfully in the United States chemical industry is the 1984 Hazardous and Solid Wastes Amendment to the Resources Conservation and Recovery Act (RCRA). Congress required that by September 1985 all generators of hazardous waste should have a written programme showing that they were actively pursuing the elimination or minimisation of their hazardous waste.

Another factor has been the desire of companies to reduce their liabilities for environmental impairment under the provisions of the Comprehensive Environmental Response, Compensation and Liabilities Act (CERCLA), better known as “Superfund”.

One of the effects of the 1984 amendment and other RCRA provisions has been to reduce the number of landfill sites and raise the price of landfill disposal-where you can get it-by factors of between two and six, depending on the type of

waste and where you are. This is why there are barges floating up and down the Coasts of the United States loaded to the gunwales with waste of various sorts looking for somewhere to dump it. It is also why any number of dodgy operators can be found in the Caribbean and Central and South America trying to interest governments of some of the poor countries, like the Turks and Caicos Islands, or totally insolvent ones, like Guyana or Haiti, in various allegedly lucrative, waste disposal programmes, either landfill on uninhabited islands or power generation through waste incineration-though the operators tend to be a bit vague on what happens to virgin forest downwind of some of these plants.

Congress also told the Environmental Protection Agency (EPA) and the Office of Technology Assessment (OTA) to report back in 1986 on how things were going. In particular on: 0 the extent to which industry was capable of minimising waste; 0 regulatory incentives and disincentives; and 0 the need for command and control regulations-in others words, fixed performance standards.

The EPA did report back and told of significant progress by industry in minimising waste, through reduction at source, recycling and reuse. It also suggested that the reduction in landfill sites would stimulate further efforts. Congress was not overimpressed as the EPA report was based largely on anecdotal information, not hard data. Congress has asked the EPA to go back and do it again, reporting in 1990 with data on the need for further regulations. This has thrown up the fact that the industry does not have good data on how plant is run.

Industry’s reaction Back in 1984 the US chemical industry was a reluctant recipient of the news of the amendment. However, the industry has now come round to the idea that it is an economically sound goal and that it offers opportunities to improve the industry’s image. It also realises that it has to seize the initiative or federal and state government will.

The chemical industry has reason to fear Government seizing the initiative. Proper waste disposal is a complex

Case study: Dow Chemical Company At its Plaquemine plant in water. Another benefit of the ! Louisiana, Dow makes based system. industrial-grade product. The project is a reduction in the i

ethylene glycol, used as an The project eliminated pH control system has ethylene glycol bottoms antifreeze and in polyester stream which previously fibre. Water is cross-flowed required biological throuah a aas stream to treatment.

and more efficient amines-

what had been a significant loss of ethylene glycol to the air. It also converts 2500 tons

of off-grade product to

resulted in fewer cleanings and a reduced ethylene glycol load to the waste-

absojb et6ylene oxide from the product and then passed to a stripper where the ethylene oxide is extracted. In the old system the water then passed to a cooling tower before being recycled. This caused a number of problems, including loss of ethylene glycol to the environment. contamination of the water from the atmosohere and eauioment . . fouling.

Dow installed a hiah- efficiency heat exch&ger and a water storage tank, and a separate cooling loop (see Figure 1) At the same time they converted the water pH control system from a cai i q t i r svstom to a cleaner

Make-up Cooling tower water -

r------ - - - - - - - - - - - I I

I I

I

I 1

I I I Pump

c---- ’ l 4 Ethylene oxide

to purification I

I Absorber I Stripper

I - A I

I I I r *

l e---- I I

*-I 1 I I F From I I reactor I i 7’ Heat exchanger I L- -- -1- - .I

I - . .

f -1 tank J ‘--Mump 1 I I

- - _- - Old system - New system

Figure 1 : Dow’s modification to its absorber water cooling saved product

matter, and regulations from amateurs could unwittingly create more problems than they solve.

matters as deciding what wastes to include and what measurements are you going to use in waste reduction: weight or volume? Should this data be normalised-that is. set in terms of waste per unit output-and is that per unit volume or weight of output? Should it be absolute-that is, waste per unit output-or relative, comparing today with next year, and doesn't that disadvantage the good companies against the sloppy on%% And if it is absolute who is going to decide what the maximum allowable level will be? Are you are going to do that for all wastes and all processes? Over what period are we measuring? It hardly bears thinking about.

If you start getting into legislation there are even such basic

Amendment problems It is worth noting that even the 1984 RCRA amendment created problems as well as solving them. Larry Fischer, of Allied Corp, at a Chemical Manufacturers Association workshop in New Orleans towards the end of 1987, pointed out that changes in the definition of hazardous waste in the amendment discouraged recycling of waste. What has happened is that any company that recycles waste under the amendment is a hazardous waste treatment or reclamation facility, and to be that you need an EPA permit. Any plant wanting to increase its recycling has to apply for revisions to its National Pollution Discharge Elimination System permits. Mr Fischer's advice to plant managers was that they have a serious think before they get into any recycling programmes in view of these regulatory problems-the complete opposite of the intention of the amendment.

The intention of Congress in 1984 was for a voluntary programme, but there are rumblings for further legislation.

A recent report, required by the Superfund legislation, to the House Subcommittee on Health and Environment said that in 1987 a third of chemicals released into the air were emitted

I by the chemical industry. The report did not include car exhausts, gases from toxic waste dumps or emissions from small sources4efined as less than around 34 tons per year-such as dry cleaners. Be that as it may, the report

I revealed that of just over l m tons of chemical released to 1 atmosphere in 1987 just under 400,000 tons were emitted by ' the chemical industry.

It is reported that the chairman of the subcommittee, Californian Democrat, Representative Henry Waxman, said that the magnitude of the problem exceeded their worst fears. The industry responded by saying that action taken after Bhopal made the survey out of date.

The EPA is preparing legislation to authorise control of air pollution.

Case study: Polaroid Dye is synthesised in solvent n a batch process, quench- 3d in an aqueous mixture to orecipitate the dye and

The reduction message h e of the most articulate apostles of "cleaner technologies' s Donald Huisingh, Professor of Environmental Sciences at \lorth Carolina State University, and at the moment Visiting hironmental Sciences Professor at Lund University in Sweden. I caught up with him at a colloquium on aOpropria!e echnologies run by Inter-Environnement Wallonie-L'Union Nallonne des Entreprises at Chateau de Lemelette near 3russels. If that sounds all a bit too much like home-wovens and sandals, it is worth noting that the sponsors included Solvay and Research Cottrell.

Professor Huisingh pointed out that waste minimisation !s xi intellectual attitude and wide implementation an sdministrative decision. Its rationale is the old English prove-b that an ounce of prevention is worth a pound of cure.

He had some interesting insights. Large savings can be just a matter of housekeeping. He point to a study in Canaca in 1982 on dry-cleaning. In a study of six dry cleaners the "best" dry cleaner cleaned 26,000 Ibs of clothes per drum 5 solvent. The "worst" got only 5500 Ibs of clothes per drum cf solvent. Looked at another way the "worst" was wasting 8% of his solvent or, in economic terms, the "worst" was payin; around five times as much as the "best" for his materials.

Process modification and materials substitution One of the most effective ways, Professor Huisingh says, is process modification and materials substitution. In other words, if you don't use it. it won't cause waste. Chevron, in Louisville, Kentucky, has a shipping-drum reconditioning facility where it cleans and repaints drums for reuse. Waste management was costing Chevron $50,000 per year. It replaced a caustic drum rinsing system with a high pressure hot water system with a closed-loop process that reuses filtered cleaning water and recovers oil removed from the drums. It also replaced a solvent-based paint system with water-based paint and water curtain filter system. This eliminated the generation of hazardous waste paint resid-. caustic, oil and water mixtures. It gave total saving of S80.WO per year, equivalent to a three year payback. It increased productivity by 200%. .

In a brief note he mentioned the Sunkiss plant in France where a thermoreactor paint drying technique was installe:: for metal finishing operations. This gave a 99% reduction ir emission of evaporated solvent, eliminated explosion risks gave better working conditions and a 99% reduction in dryng time, along with an 80% saving in energy. Payback was tw3 months.

substitution programmes running today, getting rid of a toxc Something to chew on: one of the largest materials

filtered out. It then has to be reslurried in water to remove impurities and filtered again. These processes generated two high-volume aqueous streams (see Figure 2). The first stream is fairly contaminated with organic solvents,

Waste reaction by-products and, heavy metal salts. It requires liquors Final product licenced external disposal. 7'7e second stream, althouQh Filter (cake)

-itaining a lower level of - jurities, could not be died in-house or dis- process

Figure 2: Schematic diagram of Polaroid's dye making

charged into the sewer I: also required expensive external disposal

The company found ths! the stream from the resluy- ing process could be usej t( quench the next batch f r m the synthesising process There were no equipmon: changes or additions remr- ed Cost were merely the R&D and product tes!tng

The waste disposal volume was reduced by 60.000 gallon in 1987 ZY 80.000 gallons in 1988 Annual saving on IransvY-a- tion and disposal of was5 fl 1988 were $160.000

waste and, if necessary, using a much more benign substitute, is that for chlorofluorocarbons (CFCs). Industry can move surprising fast and extremely effectively when it has its mind concentrated on a problem. Public opinion and political pressure can be powerful motivating forces.

topper tails (KATT)

Approaches for success By examining 500 case studies of firms that have successfully implemented waste reduction and risk reduction programmes through materials substitution and process modification, Professor Huisingh has identified a number of general approaches which singly or in combination can achieve the goals: 0 replace chemical processes with mechanical processes; 0 replace single-pass rinse processes with counter-current processes; 0 replace single-pass processes with closed-loop processes; 0 replace organic solvent-based inks, paints and coatings with water-based inks, paints or coatings; 0 replace acidic or alkaline treatment processes with mechanical processes: 0 replace mercury, cadmium and lead with other, less toxic substances, as components in pigments, catalysts, batteries and other products; 0 replace halogenated compounds with non-halogenated compounds; 0 install, within the manufacturing processes, advanced new technologies, such as ion exchange, ultrafiltration, reverse osmosis, electrodialysis or other processes, to effect separation of components from the process stream and to return the useful ones to the processes from which they came; 0 install new proprietary waste reduction technologies (Note: some companies successfully solved their own waste problems by developing new process technologies, patenting

Waste disposal

them and marketing a new product): and 0 install new, more accurate micro-sensors, micro- processors and other advanced process monitoring and modulating equipment, thereby making it possible to achieve, and to maintain continuously, more optimal process conditions.

Professor Huisingh says that implementation of these types of modifications has resulted in 70-100% reductions of some air emissions, water emissions and/or the production of hazardous and nonhazardous solid wastes.

Paybacks were in the range of less than one to three years and were due to: 0 decreased in raw material costs: e decreased waste management costs; 0 decreased energy costs; 0 improved product quality; 0 enhanced productivity; 0 decreased downtime; 0 decreased worker health risk: 0 decreased enviro8mental hazards; 0 decreased long-term liability for clean-up of waste materials that might have otherwise been buried; and last but not least 0 improved public image for the company.

Integrated approach Professor Huisingh also encourages recycling and reuse. But what all this leads to is an integrated approach to waste management. One of his favourite examples here is PCA International, a photographic film processor. There they were happily tipping everything down the sink after use. By installing an in-line ion-exchanger they regenerated film developer. They installed in-line reverse osmosis for rinse water and an electrostatic silver recovery unit for the fixer solution. The cost was $120,000.

Case study: Monsanto Cyclohexanone and Nitric acid Airl cyclohexanol (KA) I

4 Oxidation

KA topper .

Cyclohexane - Purge production system

t I '

Waste liquor I (waste stream 1) Refinement residue

(waste stream 2) "igure 3: The adipic acid manufacture process and the

' Lources of waste

scrubbing tower. Also bisulphite oxidises happily to sulphate to form gypsum.

Monsanto took an integrated approach to their waste problem (see Figure 4). They evaporate a portion of the waste liquor, concen- trating to over 50% organic solid, and sell the product as an alternative to adipic acid for use in FGD plant. It is

sold as AGS Mixture. The other portion of the waste liquor is used to wash the refinement residue which is subsequently burned in boiler plant in the adipic acid plant. The metals are removed from the refinement residue by an ion exchange process. Unused or unsold portions of the AGS mixture are also burned.

Waste liquor 1 I (waste stream I)

- -- - - , Flue gas

desulfurization I I I

At its Pensacola site Monsanto makes adipic acid, used in the manufacture of nylon, by the oxidation of cyclohexane (see Figure 3) There are two waste stream the waste llquor (waste stream 1 ) from the crystallisation process Which is about 25% dibasic mds, such as adipic acid. ' wnic acid and glutaric ' and the rest is water

minor impurities: and the ment residue (waste

stream 2) which is mainly organic esters and a second aqueous phase, together with metals like sodium and boron.

flue gas desulphurisation (FGD) plant to buffer the limestone slurry (see E€, Oct 1988 p36). By controlling the pH of the slurry, it makes sure the sulphur dioxide is absorbed as bisulphite which is soluble and therefore does not clog up the

Adipic acid is also used in

I , 14-1 generation

Waste containing fixer, developer and bleach went from 1.1 m gallon per year to zero.

Savings in things they didn't have to buy amounted to $360,000 in developing solution, $25,000 in fixer solution, and $780,000 in bleach solution. In addition they got $1.4m for the silver they recovered. Total savings were $2.575m. Payback was less than a month.

approach recommended by the EPA to waste minimisation techniques.

Figure 5 shows the

State of mind What should have become clear from all this is that waste reduction, like safety and quality assurance (see p97), is a state of mind. It is a state of mind that ha5 to start right at the top and permeate

r k - c -cJl=w-

0 Product substitution

0 Change in product composition

(onsite and dfsib) 5-& 0 Raw matenal substflute

for another process

0 Procedural measures 0 Loss prevention 0 Managementpractices 0 Waste stream segregation 0 Material handling

improvements 0 Production scheduling

Figure 5: Waste reduction techniques (Courtesy EPA) undiluted all the way down to the man who sweeDs the shoo -. - ~

floor. And if you think about it,' in the short-term the man who sweeps the shop floor can probably tell you more about getting results in waste reduction than the senior process engineer. Certainly in-plant personnel who have to operate the process may be a source of many good ideas.

In one case study at Polaroid, plant operators were unable to feed slurry into a centrifuge in consistent loads of proper size because of difficulties observing the level in the feed vessel. The process requires the spun-out cake to be washed in the centrifuge with acetone to remove impurities. Because of the inconsistency of the load, and therefore poor washing, the product had to be reslurried in acetone in a reaction vessel and recentrifuged.

A chemical engineer, who had spent some time in waste reduction projects, was called. She recommended a flowmeter in the feed-line. This eliminated the reslurrying process. The acetone saved by this simple step was around 31,500 gallons in 1988. giving an estimated $52,000 in savings on acetone buying and disposal.

Something to chew on: The European Council of Chemical Manufacturers' Federations (CEFIC) in its 'Summary of principles of industrial waste management" names as its first two principles waste reduction and waste recovery. Waste treatment comes at the bottom end. Most chemical companies claim to subscribe to this. What are their priorities in allocation of resources when it comes to waste?

Waste audit What may also have become clear is that before you can reduce waste you need to know what you are Poducing and how much. A surprising number of plants are extremely woolly on this. A waste audit is essential. The figures may be staggering.

Last year a report from the Institution of Mechanical Engineers reckoned that in bulk materials handling spillage was about 1% of throughput and costing British industry f200m a year (see TCE. Aug 1988 p13).

Dow, in one of its WRAP reports, mentions its plant in Louisiana producing polyethylene plastic resin pellets. These pellets are sold to processors who melt them and form them

into products. The plant produces around 445,OOO tons of pellets a year. During manufacture and handling pellets were spilt. Rainwater washed them into the Mississippi River where they floated down to the Gulf of Mexico. Wildlife-particularly birds-think they look like fish eggs, which doesn't do wildlife much good.

Dow installed a weir collection system, where the water flows under the weir, which catches these lost pellets and sends them back for reprocessing. They have also redesigned pellet package handling systems. The weir system is capturing 500 Ibs of pellets a day.

Dow has also come up with a design for a drum that empties better (see TCE. Dec 1988 p80). The company reckons that the European chemical and oil industries could reduce waste by maybe 28.000 m3 by using the drum.

Corporate steps Professor Huisingh has developed a plan of corporate steps necessary for waste reduction: 0 develop a corporate environmental policy; 0 develop waste reduction audit procedures and use them on a regular basis; 0 involve employees in incentive awards programmes to stimuiate creative solutions to waste reduction opportunities; 0 set corporate goals for waste reduction with specific percentages and timetables; 0 allocate responsibility, time and financial support for waste reduction; 0 obtain outside technical information, if necessary; e monitor and evaluate progress on waste reduction programmes; 0 regularly inform all employees of progress made in the last month, six months, year and five years; 0 update goals and timetables; and 0 remember "Success is a journey not a goal".

Implementation It IS impossible to give a detailed analysis of how to tackle implementation of a comprehenslve waste reduction

- _.

The recognised need to mmimtse waste

0 mmanagement commit"!

0 Ormnse essessment m r a m task force 0 set overall assessment program goals

I Assessment organisatio nd commlment to proceed

A.Ser;unerdPhm 0 Collect process and facilty data 0 Priontise and Select assessment targets 0 Select people for assessment teams

Review data and inspect ste 0 Generate opbons assessment targets 0 Screen and select opttons for further study

Select new

and previous options

I -MdydSpharre 0 Technical evaluation 0 Economic evaluation

Select options for imdementation

0 Justify projects and obtain funding 0 Installation (equipment) 0 Implementation (procedure) 0 Evaluate performance.

.) Successfully implemented

wade minimisation Drojects

'igure 6: The waste minimisation assessment procedure Zourtesy EPA)

'rogramme, as so much depends on company ulture-whether power and decision making and taking is entralised or devolved. From reading company reports on 1eir.efforts some points seem universal (see Figure 6). Du Pont says,"The concept of waste reduction must

ecome institutionalised to the point where it is a primary hoice for action in any plan. Once the target of waste ?duction has become ingrained within the entire rganisation, more progress will be made, especially by the usiness and product managers". The general idea is to have a senior management steering

?am and then a series of project teams assigned to specific roblems. On forming project teams Hoechst Celanese at :oventry, Rhode Island. notes that each department on the teering team will want a member of its department on the roject team. Resist this. 'Choose only the personnel who can ontribute in the most effective manner", it says. "Team iembers could then call on key personnel from the various epartments, on an as-needed basis, to participate in the agnostic and remedial journeys." One study also recommended getting in someone from

cltside, someone who will ask very basic questions as to Nhy do you do it like this?" and who will not be fobbed of fith, 'Because that's the way we do it round here." In the Hoechst Celanese report it notes on one case study,

The long-held view on standard filter aid additions and effect n product quality were reviewed in light of new data. The ?sults of the production foreman's tests conclusively showed 0 Ib additions could be either totally eliminated or drastically ?duced without adversely affecting product quality. The medy was simple and the benefits astounding! With one :--)ke. the largest waste-generating department became the

m d smallest producer of clarification residue." nce a team has completed a project disband it and form .v one to tackle another project. New teams have new

ideas, and it gets more people involved. It also means teams don't have time to get divorced from what is actually going on in the plant.

From what I have written I would not wish you to think that active waste reduction programmes are peculiar to the United States. They are not. A lot of work is going on in Europe-in Scandinavia. in the Netherlands and in Germany. In Sweden there is the Landskrona Project where, in Landskrona. a number of companies in graphics, metal working and the chemical industry are co-operating in a project to help smallei firms which may find it difficult to collect and evaluate information about the best available approaches and technologies to reduce their waste.

Huisingh: "The pessimist sees the difficulty in every opportunity; the optimist, the opportunity in every difficulty." lG#ll

And a final th'ought from L P Jacks, courtesy of Professor

Further reading Waste minimization Opportunity assessment manual (EPN625/7-88/003), and Waste minimization, environmental quality with economic benefits (EPN530-SW-87-026). United States Environmental Protection Agency, Hazardous Waste Engineering Laboratory, Cincinnati, Ohio 45268, USA. For WRAP case studies contact Dow Chemical Co, Environmental Quality Department, 2030 Willard H Dow Center, Midland, Michigan 48674, USA, tel(517) 636-2538. For 3M's Ideas case studies contact Environmental Engineering and Pollution Control Department, 3M, P 0 Box 33331, Building 21-2W, Saint Paul, Minnesota 55133, USA, te (612) 778-4791. For Du Pont case studies Wasteline, editor Don Verrico, External Affairs Department, Du Pont. Wilmington. Delaware 19898, USA, tel(302) 774-0054. Huisingh 0, Martin L, Hilger H and Seldman N, Proven profits from pollution prevention, Institute for Local Self-Reliance, 2425 18th Street NW, Washington, DC 20009, USA, tel (202) 232 4108. price $25 plus $5 p&p. Gardner, L C and Huisingh D, Alternative approaches to waste reduction irrmateris coating-processes, Hazardous Waste & Hazardous Materials, vol4, no 2 1987, p177, May Ann Liebert, Inc. British case studies: Robinson S (ed), Healthier profits-business, success and the green factor, The Environment Foundation, 15 Minories, London EC3N lNJ, telO1-480 6137, price f5.95. How it's done: Hollod G J and McCartney R F, Waste reduction in the chemical industry: Du Pont's approach, Journal of the Air Pollution Control Association, vol38, no 2, Feb 1988, p 1 74. Fro" C H, Callahan M S. Freeman H M and Drabkin M, Succeeding at waste minimization, Chem €ng,.vol94, no 12, Sep 14, 1987, p91. Hoechst Celanese in Rhode Island used the Juran Institute approach: Enander R T and Nester D J, A structured approach to solid waste management, Chem Eng Prog, Apr 1988, p27. To understand the Juran Institute approach there is an article in the same issue on p25. 4t the annual meeting of the AlChE last year, 27 Nov-2 Dec. a lumber of papers on waste reduction were presented.

Further information Professor Donald Huisingh can be contacted at the University Df Lund, TEM. Box 62, Asumsgatan 38,275 22 Sjbbo, Sweden, tel Sweden 416 273 00. fax Sweden 46 12 30 06 He ias plenty of information on the Landskrona project Vetwork for Environmental Technology Transfer, 25 Square de Ueeirs, 8-1040 Brussels, Belgium, tel Belgium 2 51 1 2462, [ax Belgium 2 51 1 2522

89-69.4

VOC EHIS i IONS CONTROL OR ELIHINATION FROH COATING OPERATINGS - THE 3\ POLLUTION PREVENTION PLUS PROGRAH

KEITH J. NILCER

3M COMPANY S i . PAUL ~ ~ I N N E S O T A

AIR & W . MANAGEMENT A S S O C I A T I O N

SINCE 1907

For Presentation at the 82nd Annual Meeting & Exhibition

Anaheim, California June 25-30,1989

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INTRODUCTION

Thirteen years ago 3M unreiled a program called Pollution Prevention Pays (3P). =e goal of the program was to eliminate or reduce sources of polldtion in 3M products and processes. With this program, worldwide annual releases of air, water, sludge, and solid waste ;ollutants from 3M facilities have been reduced by nearly 450,OOC tona. Earlier this year, 3M initiated a new phase of 3P, a five-year plan called Pollution Prevention Plus (3P+). POllUtiOn control equipme3t to reduce our annual hydrocarbon emissions by more than 55.000 tons. This effort is entirely voluntary and represents reduction beyond compliance with state and federal regulations.

At its heart is a $150 million investment in air

In order to reduce hydrotr:bon emissions for 3P+, implementation of VOC emissions control :r elimination from coating operations is required. With coatin; operations in 15 operating divisions and 20 3M facilities needrng to be addressed, an extensive program to investigate VOC cnissions control or elimination alternatives was initiated. control and elimination sxategy was developed for the 3P+ Program. a tremendous challenge, brt with an organized team approach to selecting emission control or elimination technologies close to realizing the enrfronmental benefits of this program.

Based on this program, an overall VOC

The task of organizing a program of this magnitude was

This paper will provide ar. overview of the history of 3M emission controls and aliaination technologies, the background and development of the 3P* Program along with the program guidelines and goals, and the Ctvelopment of control and elimination Strategies for the 3P+ Prqtam. the selection of control or elimination technologies will be provided. the 3P+ Program will be discussed.

Technical considerations for

Also, the contr?l strategies being implemented for

HISTORY OF 3H VOC EMISSIOK5 CONTROL AND ELIMINATION STRATEGIES

The control or elimination of VOC emissions from coating operations is not new to 3E. application of many differt3t VOC emission control and elimination technologies fc: nearly 30 years. We have experience in both U.S. ant O . U . S . (outside U.S.) facilities.

3M has been involved in the

2

UP to thi have resL equipment includes adaorpt iC (solvent

VOC Emisc

Numerous both in 1 oxidatior ox idat io1 and four some of ' there is inq cont provides changes operatio

With SLA oven is SLA inci recovers requ i r em utilize is that than the port ion

Carbon a operatic experier ope rates and nine The key recover f ac i 1 it\ on-s ite . sold to

Both in* solvent where tl solvent gas atmi much hi, convent the SLA

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Up to this point, the majority of the 3M emission reductions have resulted from the application of VOC emission control equipment. 31 experience in emission control applications includes the following technologies: thermal oxidation, carbon ad.orption, inert condensation, noninert condensation, and SLA (solvent laden air) incineration.

VOC Emissions Controls

Numeroua applications of thermal oxidation equipment are present both in U.S. and O.U.S. facilities. Various types of thermal oxidation equipment (recuperative, regenerative, and catalytic oxidation) have been utilized. At present, six U.S. facilities and four 0.U.S facilities have thermal oxidation equipment. Some of thane facilitien have more than one thermal oxidizer as there is more than one coating operation at the facility requiring control. Utilizing thermal oxidation at these facilities provides the ability to handle a wide range of solvents and changes in solvent mixtures as products vary in the coating operations.

With SLA incineration, SLA from the coating operation drying oven is exhausted to the facility boilers for direct combustion. SLA incineration not only reduces the WX: emissions, but recovers the fuel value of the solvents and reduces fuel requirements in the boilers. Currently, three U.S. facilities utilize SLA incineration. The main problem with this technology is that the boiler air flow requirement is substantially lesr than the coating operation SLA volume. Therefore, only a portion of the VOC from the coating operation is controlled.

Carbon adsorption technology is considered a standard unit operation for VOC control of SLA. 3M has a great deal of experience in carbon adsorption technology. Presently, 31 operates five carbon adsorption systems at three U.S. facilities and nine carbon adsorption systems at eight 0.U.S facilities. The key to carbon adsorption technology is the ability to recover the solvent from the coating operation for reuse at the facility. In moat cases, 3M does recover the solvent for reuse on-site. In the other applications, the recovered solvent is sold to a solvent recycler.

Both inert and noninert condensation systems have been used for solvent recovery at 3M. Inert gas condensation is a process where the oven in the coating process is used to concentrate the solvent by recirculating the oven gases. The use of an inert gas atmosphere eliminates the hazard of explosion and allows for much higher solvent concentrations in the oven than a conventional air lrntaining oven. The solvent is condensed from the SLA and the stream is reheated and returned to the oven.

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Currently, three of our U.S. facilities utilize inert condensation for solvent recovery. Noninert condensation utilizes a conventional air containing oven with solvent concentrations below the LFL (lower flammable limit) of the solvents. Due to the lower solvent concentration in the oven, much colder temperatures must be reached to provide for solvent condensation. Only one U.S. facility has a noninert condensation system.

VOC Elimination Technologies

3M has also been involved in VOC elimination technologies to either eliminate or reduce the need for solvent in its coating operations. Historically, solvent processes were developed and offered new and different properties. Products were developed from these processes because of performance, productivity, quality, and economics, as well as for emissions control.

Numerous solvent elimination technologies have been investigated and utilized by 3M in our coating operations. Those technologies include the following: hot melt extrusion, extrusion and coating of reactive systems, waterborne coating, surface and polymeric modification for primer and saturants, high solids coating, and other coating technologies including patterned and vacuum deposited coatings.

The utilization of these elimination technologies is spread throughout the company both U.S. and O.U.S. More than 18 operating divisions utilize these various VOC elimination technologies in their coating operations.

POLLUTION PREVENTION PLUS

The idea for 3P+ came out of regular management of 3M's environmental goals. decided that our emission reductions, though significant, did not go far enough. level of environmental concern. we estimate that we can eliminate or control more than 85% of 3M's U.S. air emissions by mid-1992 with further 3P reductions after that. are in 3P. phase-in of new controls with over 80% of the O.U.S. VOC emissions estimated to be controlled or eliminated.

In looking at past results, management

Thus, 3P+ was introduced to reflect a higher With 3P and 3P+ both in place,

O.U.S. facilities are included in 3P+, just as they However, they have until mid-1993 to complete their

The 3M Operations Committee, our top level management group, approved the 3P+ Program in mid-1907. of action, which was instituted despite full regulatory compliance, management propelled 3M into a new era of VOC emission control and elimination. corporate mandate, the 3M Environmental Engineering and Pollution Control group formed a team t o organize a n air emission reduction plan for the company.

With this voluntary plan

In order to respond to this

All 3M facilities were

evaluate volume t m0nt of em14: These f b

three g:

This Pr control msnt ar of the are alr 1990. ment ar smaller by mid- O.U.S.

3p+ Gui

Under 2 additic that ea areas t instal? polluti revise to insL quireme credit L tion tc have s

A tota' mill io. This i. tons o preven 110,oo new co

The wo signif affect emissi

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evaluated based on VOC emissions and related factors including: volume of VOC emitted, plant location (attainment or nonattain- ment area), population near facility, odor complaints, toxicity of emissions, economics, and pending regulatory requirements. There factors were used to prioritize all 3M facilities into thr8e groups of either A, B, or C priority.

This prioritization allows an organized approach to VOC emission control or elimination. 3 M plants operating in ozone nonattain- ment areas are targeted to receive the first 3P+ controls. Some of the controls €or the first group of these plants ( A Group) are already in place with the remainder to be on-line by early 1990. Controls at the larger emitting facilities in tho attainment areas will be phased in through mid-1990. Controls at the smaller 3M facilities covered by this program will be installed by mid-1992. A similar control schedule existed for the 3M O.U.S. facilities with a mid-1993 final control date.

3P+ Guidelines and Goals

Under 3P+, 3W will, between 1988 and mid-1992: 1) install additional control equipment at all 3M facilities in the U.S. that emit 100 tons or more of VOC even if the facilities are in areas that already meet government air quality standards! 2 ) install the best available control technology (BACT) on all new pollutant sources that annually emit 40 tons or more of VOCt 3 ) revise bubble compliance plans and eliminate the use of netting to insure that individual aources meet the new 3M control requirements: 4) donate all or part of the air emission reduction credits that result from the new emission controls or elimination to local permitting agencies. The 3M O . U . S . facilities have similar guidelines.

A total 3M investment in the 3P+ Program of $150 million, $120 million which will be spent on U.S. facilities, is estimated. This investment will achieve a reduction of more than 45,000 tons of VOC emissions per year in the U.S. To date, 3P has prevented or reduced air emissions in the U.S. by just over 1lO,OOO tons per year. O.U.S. emission reductions due to the new controls will amount to approximately 10,400 tons per year.

The worldwide impact on 3M facilities with coating operations is significant. In the U.S., 85 coating operations will be affected by this program. A breakdown of U.S. goals for VOC emissions reduction is as follows:

A Group - 10,000 tons per year B Group - 25,000 tons per year C Group - 11,000 tons per year

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At O.U.S. facilities another 24 coating operations will be affected by the program. been set for 3M O.U.S. facilities as follows:

VOC emissions reduction goals have

A Group - 3,400 tons per year B Group - 5,500 tons per year C Group - 3,600 tons per year

DEVELOPMENT OF CONTROL AND ELIMINATION STRATEGIES FOR 3P+

In order to meet the 3P+ guidelines and goals, control strategies were developed for each 3M facility. Facility teams were established for each of the 3M facilitiea with representatives from various disciplines in the operating division organization including project engineering, process engineering, laboratory, manufacturing, and environmental, the plant VOC emissions and determined the most appropriate control or elimination strategy for the facility.

The facility teams studied

The evaluation conducted €or the selection of control or elimination technologies and the initial 3P+ controls which are being implemented are discussed in this section.

Selection of Control Technology

Many different technical considerations required evaluation for the selection of emission control technology. capital cost and operation and maintenance cost factors were evaluated to determine the economics €or the control technologies.

In addition, both

The major technical conaiderationa identified and evaluated were as follows:

Solvents Concentration Air Volume Temperature Other SLA Constituents Water Pollution Control Requirements

Regarding solvents, a number of factors were considered. included an evaluation of the solvent mixture where multiple solvent8 were used in the coating operations. Factors such as whether the solvent is miscible in water, whether the solvents form an azeotrope with water or each other, and the boiling points of the solvents in a mixture were considered regarding the potential reuse of the solvents after recovery. Racover- ability of the solvents was important to 3M a5 an economic return on investment can be realized through the recovery and reuse of solvents back in coating operations.

These

Another factor is 6

1 the cost Of , solvents iE ! f u e l value 1

The concent as well as

, choosing a , technoloQi' ! oxidation

the solvent . critical tc . facilities

coater over size and cc

The presenc may cause 1 presence of solution mi in a carbor operation : determine sacr if ic ia' contaminan'

Uater pol11 Control tei adsorpt ion pounds of 1

the solven the wastew the solven generated air in the recovery. be require

!

Each of th greatly af The same t impact dur add it ion, must be co

Energ t a b o r Recov naint EqUiF

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the cost of the solvents being used. The recoverability of the solvents is an important factor for the expensive solvents. The fuel value of a solvent must also be considered when evaluating cmbustion technologies for control.

*.e concentration of the solvent in the SLA from the coater oven AI well as the total air volume are important factors in choosing a control technology. The suitability of certain technologies (e.g., using recuperative vs. regenerative thermal oxidation equipment) is highly dependent on the concentration of the solvents in the SLA. In addition, the total air volume is critical to the capital cost of the control equipment. Host 3M facilities initiated programs for reducing air flows from the coatec ovens by using air recirculation in order to reduce the rize and coat for control equipment.

The presence of other constituents in the SLA Crom a coatar oven may cause fouling problems with a control technology. The presence of particulates or high boilers from the coating solution materials may foul heat exchangers or activated carbon in a carbon ad8orption system. Sampling the SLA from a Coating operation should be conducted prior to equipment selection to determine the potential for fouling. Filtration equipment or racrificial beds may be required to remove any potential contaminants in the SU.

Water pollution control requirements must also be considered €or control technologies where a wastewater is generated. In carbon adsorption systems with steam desorption, approximately four pounds of water is generated per pound of solvent recovered. If the solvent is soluble in water, some solvent will be present in the wastewater after decanting with a concentration dependent on the 8oIvent solubility in water. Wastewater may also be generated from condensation systems as the water vapor from the air in the oven is condensed along with the solvents during recovery. In both cases, water pollution control equipment may be required for wastewater pretreatment prior to discharge.

Each of the technical considerations discussed above also greatly affects the capital cost for emission control equipment. The same technical factors must be evaluated for their economic hpact during the evaluation of a control technology. In addition, the operation and maintenance cost factors given below must be considered:

Energy Labor Recovered Solvent Savings Maintenance Requirements Equ i pme n t De p re c i at ion

7

and the flow througl tal flow pa thermal oxi' (0-958 the ri nith low SO

Catalytic t rutface rat system, oxi mtely 600'

89-69.4

VOC CONTROL TECHNOLOGIES FOR 3P+

T b r e are numerous VOC emission control technologies available. Technologies for either direct combustion or recovery of solvent were considered depending on the specific application. A list of the VOC emission control technologies evaluated €or the 3P+ Program is as follows:

Thermal Oxidation SLA Incineration Inert Gas Condensation Cold Condensation Carbon Adsorption Polymer Adsorption Liquid Absorption

All of these control technologies are commercially available. However, both polymer adsorption and liquid absorption are emerging technologies with no 3M experience and very little industry experience.

Thermal Oxidation. Thermal oxidation is the direct combustion of SLA from an oven exhaust. Thermal oxidizers are designed to maximize solvent destruction, SLA from the oven exhaust is vented directly to the thermal Oxidation equipment where it is oxidized to an acceptable chemical form and vented to the atmosphere. Since the oven exhaust has a solvent concentration below the LFL, the oxidizer must be supplemented through solvent enrichment, supplemental fuel or thermal assistance.

Thermal oxidation equipment is also designed to reduce energy cost by maximizing thermal energy recovery. types of thermal oxidizers considerd were recuperative, regenerative, and catalytic.

Recuperative thermal oxidizers oxidize solvent laden air by direct combustion at temperatures of approximately 1400OF. The method of heat exchange used to preheat incoming oven exhaust is direct heating from the oxidizer burners using heat exchangers. Either plate, round tube, or undulated tube heat exchangers are commonly used. Thermal efficiency of these heat exchangers is normally between 3 5 4 0 % efficient, with the cost of the heat exchanger increasing exponentially with efficiency.

Regenerative thermal oxidizers oxidize the SLA by direct combustion at temperatures of approximately 14OO0F, but use large ceramic beds for heat exchange. SLA is heated by passing through a hot ceramic (or other media) bed while solvent combustion air heats a second bed. When the first bed can no longer heat the incoming streams sufficiently to cause oxidation, the flow of gas is reversed so that the stream is heated by a second

The three basic

8

efficiency there have in catalyti

the main di potential f onergy inte appropr iate

The main ac handle a w : air flows,

SLA Incine. of sLA fror econom ics solvent ani for ductin also impac minimum.

Experience tions are are capabl oxidation oxidation boiling sc

Inert Gas recovery 1 eliminate trations i by passim The solve! reheated I

Inert gas for new c condenser

89-69.4

bed and the first bed is heated by thermal exhaust. The SLA flou through the hot bed may be either in a vertical or horizontal flow pattern depending on the system design. Regenerative thermal oxidaeion systems are normally designed to operate at 80-951 thermal efficiency. Regenerative systems are preferred with low solvent concentrations in the SLA (less than 151 L F L ) .

Catalytic thermal oxidation oxidizes the solvent on a catalyst surface rather than by direct combustion. With this type oE system, oxidation occurs at a much lower temperature (approximately 600eF) . With oxidation at a much lower temperature, high efficiency of heat exchange systems is not required. However, there have been problems with poisoning and fouling of catalyst in catalytic oxidation systems.

Tbe main disadvantage of thermal oxidizers is that they have no potential for recovery of solvents. Also, they are generally

T g y intensive. These advantages made thermal oxidation the ropriate technology for a number of applications.

the main advantages of thermal oxidation is the ability to handle a wide range of solvents, changes in solvents, changes in air flows, and changes in solvent concentrations.

SLA Incineration. SLA incineration involves direct combustion of SLA from the coater oven in the facility boilers. The economics for SLA incineration depend on the fuel value of the solvent and input SLA temperature along with the capital cost for ducting the SLA to the boiler. Solvent content of the SLA also impacts the economics and should exceed 8% LFL as a minimum.

Experience at 3M has shown that most boiler burner configura- tions are adaptable to SLA incineration. Generally the burners are capable of complete oxidation when using SLA. Incomplete oxidation can result in the release o t aldehydes and other low oxidation states which can cause odors. In addition, some high boiling solvents can build up a residue in burner tubes.

Inert Gas Condensation. recovery uses an inert gas atmosphere (less than 8% oxygen) to eliminate the hazard of explosion which allows solvent concentrations above the LFL in the coater oven. Solvent is collected by passing a small side stream of oven SLA through a condenser. The solvent is condensed from the SLA and the gas stream is reheated and returned to the oven.

Inert gas condensation is most economical for solvent recovery for new coater oven applications. An inert gas oven with a Condanser costs approximately 10% more than a conventional oven.

9

Inert gas condensation solvent

09-69.4

T h e r e f o r e , s o l v e n t r e c o v e r y c a n b e i n s t a l l e d f o r a minimal i n i t i a l c a p i t a l e x p e n d i t u r e . A l s o , t he s o l v e n t r e c o v e r y p r o c e s s As t h e n p a r t o f t h e c o a t i n g p r o c e s s . The r e t r o f i t t i n g o f a con- v e n t i o n a l oven f o r i n e r t gas is much more d i f f i c u l t . I n addi - t i o n to t h e p h y s i c a l p r o b l e m s o f a n o v e n r e t r o f i t , there is t h e e x t e n d e d coater downtime r e q u i r e m e n t f o r t h e r e t r o f i t . T h i s h a s l i m i t e d t h e a p p l i c a t i o n o f i n e r t gas oven r e t r o f i t t i n g a t 3M.

A major p o t e n t i a l b e n e f i t f rom i n e r t g a s oven s y s t e m s is p r o d u c t q u a l i t y improvement. s o l v e n t c o n c e n t r a t i o n s f o r d r y i n g r e d u c e s d r y i n g t i m e and r e d u c e s p i n h o l e and b l i s t e r e f f e c t s i n t h e c o a t i n g s .

Cold C o n d e n s a t i o n . c o n d e n s a t i o n s y s t e m s a v a i l a b l e f o r c o n d e n s i n g SLA f rom a conven- t i o n a l oven which were e v a l u a t e d . t h e t e m p e r a t u r e o f t h e SLA down to v a r i a b l e t e m p e r a t u r e s (as low as -120'F) to c o n d e n s e t h e s o l v e n t .

Low t e m p e r a t u r e r e f r i g e r a t i o n s o l v e n t r e c o v e r y is o n e method f o r cold c o n d e n s a t i o n . Freon is g e n e r a l l y used as t h e r e f r i g e r a n t i n t h e s e s y s t e m s . g e n e r a l l y u s e d w i t h a d u a l h e a t e x c h a n g e s y s t e m t o p r o v i d e f o r f r o s t c o n t r o l . s o l v e n t , it f r e e z e s up d u e to water p r e s e n t i n t h e SLA. A t t h e same time, t h e o t h e r h e a t e x c h a n g e system is d e f r o s t i n g by r e c i r c u l a t i n g warm r e f r i g e r a n t t h r o u s h t h e h e a t e x c h a n g e r . o r d e r t o a c h i e v e v e r y l o w t e m p e r a t u r e s ( l ess t h a n -60.F) c a s c a d e r e f r i g e r a t i o n is g e n e r a l l y r e q u i r e d . T h e r e f o r e , t h i s t e c h n o l o g y h a s n o t been p u r s u e d by 3M.

A i r c y c l e s o l v e n t r e c o v e r y b a s e d o n the B r a y t o n c y c l e is a n o t h e r c o l d c o n d e n s a t i o n t e c h n o l o g y . c o m p r e s s o r c o n s i s t i n g o f a compressor wheel and e x p a n d e r wheel mounted on a common s h a f t . and p r o c e e d s t h r o u g h a series o f h e a t e x c h a n g e r s b e f o r e e n t e r i n g t h e e x p a n d e r wheel . Cold t u r b i n e e x h a u s t a i r e n t e r s t h e oppo- s i te s i d e o f t h e h e a t e x c h a n g e r s a n d r e t u r n s to t h e coater oven. S u f f i c i e n t h e a t is removed from t h e c o m p r e s s o r d i s c h a r g e a i r to d r o p t h e t e m p e r a t u r e as l o w a s -120.F. The heat t r a n s f e r r e d to t h e t u r b i n e e x h a u s t a i r p r e h e a t s t h e a i r r e t u r n i n g to t h e oven.

3M h a s t h r e e p a t e n t s on t h i s t y p e of s y s t e m a s w e l l as a Record of I n v e n t i o n . However, t h e a i r c y c l e s y s t e m is n o t commerc ia l ly a v a i l a b l e . Carbon A d s o r o t i o n . Carbon a d s o r p t i o n h a s been used Cor s o l v e n t r e c o v e r y Cor o v e r 50 y e a r s . two-cyc le p r o c e s s . T h e r e is an a d s o r p t i o n c y c l e where t h e s o l v e n t is removed from t h e SLA u n t i l t h e a d s o r p t i o n c a p a c i t y oE t h e c a r b o n is d e p l e t e d . A f t e r a d s o r p t i o n is c o m p l e t e d , t h e

I t has been shown t h a t t h e u s e o f h i g h

T h e r e are b a s i c a l l y two t y p e s of d i r e c t

B o t h t y p e s o f s y s t e m s r e d u c e

A c l o s e d c y c l e s y s t e m f o r h e a t r e c o v e r y is

As o n e h e a t e x c h a n g e s y s t e m is c o n d e n s i n g

I n

T h i s s y s t e m u t i l i z e s a t u r b o

The SLA e n t e r s t h e compressor wheel

T h i s t y p e o f s o l v e n t r e c o v e r y is a

10

i

I

t i i

!

!

1 carbon bed 01s is used carbon a d s o cont inuous

nost carbon bed s u p p o r t vessels 01: systems) mz annular car problems, 5 cons t r u c t e c a v a i l a b l e , c o s t f o r t l c o s t of t h l Flu id i zed ' bed for a n

Polwner Ad u t i l i z e s a c o a t e r ove Sweden. C using the i

f l u i d i z e

One o f t h e adsorb Wat a p p l i c a t i c a d s o r p t i o r n a t e l y twc polymer i: approxima polymer b c o s t . I n polymer f is v e r y h

Liquid A t t i o n scru i n e r t , h i process i e x t r a c t a r i n d u s t r y opera t io1

The l i q u e n g i n e e r h e a t t r a exchange through i n v o l v e

-.

89-69.4 89-69.4

carbon bed goes into a desorption cycle where steam or hot inert oa~,is used to remove the solvent from the carbon. carbon adsorption system contains multiple beds to insure continuous operat ion.

nost carbon adsorption systems are designed with a fixed carbon bed supported by a screen inside a vessel. Separate horizontal vessels or a single vessel divided into chambers (for small systems) may be used. In the past, rotary carbon beds and annular carbon bed designs have been used. Howeverr due to problems, systems with these designs are no longer being constructed. Fluidized bed carbon adsorption systems are also available, but a specialized spherical carbon is required. The cost for this spherical carbon is approximately five times the cost of the pelletized carbon uaed in fixed bed syatems. Fluidized bed systems did not offer any advantages over fixed bed for any 3 M application.

Polymer AdsorDtion. There is a new technology available which utilizes a polymer for adsorbing solvent from the S W from a coater oven. The polymer was developed by Nobel Chematur of Sweden. Currently, they market only polymer adsorption systems using their polymer and not the polymer. These systems utilize a f,luidized bed design.

One of the main features of the polymer is that it does not adsorb water. This offers many advantages in solvent recovery applications where water is present and causes problems with adsorption or as an impurity in the recovered solvent. Approxi- mately two pounds of polymer is required per scfm of SLA. The polymer is approximately 1 millimeter in diameter and costs approximately $14 per pound. With this high polymer cost, the Polymer becomes a major part of the adsorption syatem capital cost. In addition, if there is any fouling or loss of the Polymer from the adsorption system, the polymer replacement cost is very high compared to carbon.

Liquid Absorption. tion scrubbing to remove solvent from a SLA stream using an inert, high boiling, organic liquid as a collection media. This Process is based on Henry's Law Constant for solvent in an extractant liquid. However, there is very little experience in industry with this technology for solvent recovery from coating operations.

The liquid absorption systems utilize simple chemical engineering unit operations of gas absorption, distillation, and heat transfer. The SLA from the oven is cooled by a heat exchanger, scrubbed by the absorption liquid, and recovered through distillation. Major applications for these systems involve the recovery of chlorinated solvents and ketones.

11

A standard

6

Liquid absorption systems utilize absorp-

.-a 1 .j' process ~f a con- n addi- 0 is the This has

at 3M.

3 ?roduct 3 igh .i

:rod for ;2rant -. 1s :t for

.L.Z the

. In Z'lscade

-.,

-.>010gy

::. of

89-69.4

VOC Elimination Technologies For 3P+

The best method for the reduction of VOC emissions is the 'elimination of hydrocarbon solvents from coatings. technology to eliminate solvents on a scale and time schedule consistent with 3 M ' s emission control needs does not currently exist. is required for future solvent emission reductions at 3H. However, following is a synposis of solvent elimination technologies being investigated or used at 3M.

However, the

Further development of solvent elimination technologies

Hot Melt. adhesives i 3M. Hot me

Hot melt process technology to deliver 100% solids n pressure sensitive applications was pioneered by mlt is a process where solid adhesives or polymers are

extruded in a coatable form onto a web or other substrate. Since solvents have been removed prior to extru~(lion, there are essentially no solvent emissions. have been used by different operating divisions at 3M in their coating operat ions.

Various hot melt adhesives

Reactive Systems. directly produced from monomers or low molecular weight oligomers. Instead of using a chemical initiator, the linking of monomers into long polymer chains and crosslink networks is accomplished in nonchemical ways such as radiation activation. Radiation cure coatings are applied using conventional coating and cured by either ultraviolet or electron beam irradiation. The irradiation initiates free radical polymerization to dry the liquid coating into a solid continuous film. This is accomplished without using volatile solvents. Various reactive systems have been utilized by 3N.

In reactive systems, polymic coatings are

Waterborne. By the mid-1990's waterborne coating is predicted to become the predominant form of coating in the coatings industry. small amount of hydrocarbon solvent to plasticize resin particles and allow for drying to a continuous film. However, the performance of waterborne coating systems is often not comparable to solvent based coating in quality.

Waterborne coatings are generally 80-90% water with a

3M has waterborne coating experience beginning in the 1950's. Various applications for waterborne coatings have been developed.

Other Coatinq Technoloqies. technologies to reduce or eliminate solvent usage. include increased solids, reduce coating weight, patterned coating, vaccum deposition, and powder coatings. High solids coating to reduce solvent usage has been successful for 3M. Also, reduced coating weight has been utilized by a number of divisions to reduce hydrocarbon soLvent usage.

3H has also explored other coating These

I

i .,:Jrant tre j .*:~sions.

-4: inqs ?C 1 ,,rcnsivelY . . , -y applica

sased on ths

:.te frame i :r:ili t ies I :-crmal oxic

' .-rtalling 2 ! Ylorinated . :-crmal oxic

:r:ilities civent r e a

, :: some the. I -cse is no! . ;::ority grc

a< 8 Grout?

3 C L U S I O N

-8 has ente . ::zn has be

-eu envicon 1 :erefore, x establis rslvents fr :-a cost of *:aipment.

5grams €0 &:* require :: be succe - 3 to achie -:traduced :we9 tment Z~ective. %ring devc un bring n effects. 7 ?event ion

NOTE 11

'h the new -tion rig

'Iokrd by thr

12

89-69.4

primer and Saturant Technologies. 8 r ~ celatlvely low level emitters, they are significant tantributers to solvent emissions due to their broad use.

Although surface treatments

&vera1 nethods have been developed to achieve surface and 8rtutant treatments which eliminate or reduce solvent usage and .atssions. These methods include surface modification, thin Coatings, polymeric modification, and saturants. .~tensively involved in these technologies and has developed -any applications for them.

)P* Control Strategy

erred on the evaluation of VOC control and elimination technologies, control strategies have been developed tor the A and B Group facilities in the 3P+ Program. Due to the short time frame involved with installing controls at the A Group facilities, five of the seven facilities will be installing thermal oxidation equipment. lnstalling liquid absorption equipment for the recovery of . chlorinated solvents. The B Group facilities will utilize both thermal oxidation and carbon adsorption. Three of the six facilities will have carbon adsorption equipment installed for solvent recovery with reuse of the recovered solvent in addition 10 some thermal oxidation equipment where solvent recovery and reuse is not feasible. The other three Eacilities in the B priority group will utilize thermal oxidation exclusively.

:ONCLuSIOS

tion has become a corporate mandate. The 3P+ Program has Set a new environmental agenda for the 3M operating divisions. Therefore, VOC emission control and elimination strategies must

solvents from coating operations, we will be forced to live with the cost of installing and operating additional control equipment.

3M has been

The two other facilities will be

has entered a new era where VOC emissions control or elimina-

estabrished. Until we can find new ways of eliminating

for solvent elimination and solvent recovery with reuse required for the overall 3M VOC emissions reduction strategy

be successful in the future. 3W's ongoing development goal to achieve 25% of its revenue each year from products

!ntroduced in the previous five years. We have increased our investment in research and development company wide to meet this objective. during development, when it is most cost effective to do so, we can bring many new products to market with minimal environmental effects.

Pays (3P) Program and the coating industry.

By seizing the opportunity to minimize pollution

This is the next big challenge for the 3H Pollution

NOTE TO E D I T O R S

13 b r tho now federal copyright law, 8blhtlon rights to this paper are

by the author(8).

?

A 1

Title Source Reduction of Chlorinated Solvents: A Multimedia Approach

Author Azita Yazdani, Project Engineer Source Reduction Research Partnership 1052 West Sixth Street, Suite 432

Los Angeles CA 90017

"Prepared for presentation at AIChE Annual Meeting, San Francisco, CA, Novetriher S-10, 1989"

"Copyright 8 Azita Yazdani"

"Date November 1989".

"URPUBLISHED"

"AIChE shall not be responsible for statements or opinions contained in papers or printed in its publications"

A2

Source Reduction of Chlorinated Solvents:

A Multimedia Approach

The chlorinated solvents, a class of interrelated

chemicals is currently under regulatory scrutiny for a variety

of reasons.

the industry, however, the largest uses are in industrial

cleaning and dry cleaning applications.

thousand metric tons (mt) of- chlorinated solvents are used in

industrial cleaning and about 112 thousand metric tons in dry

These solvents are used in many diverse sectors of

- Approximately 285

cleaning applications* * 2.

- All the five major chlorinated solvents,

trichloroethylene (TCE), perchloroethylene (PERC),

l,l,l-trichloroethane (TCA), methylene chloride (METH), and

1,1,2-trichloro, 1,2p2-trifluorocarbon (CFC-113) are used in

industrial cleaning applications.

cleaning industry and to a much smaller extent CFC-113 and TCA.

Mainly PERC is used in dry

In the course of the two year study, the Source

Reduction Research Partnership has studied the industrial

processes where these solvents are used, and has examined

various measures that can lead to reduction in use of these

solvents in the applicable industries.

c

- 2 -

Below, a short description of the two processes

discussed in this paper have been provided.

PROCESS DESCRIPTION.

Solvent Cleaninq

Solvent cleaning is mrmally required before assembly,

A3

fabricating, painting or welding.

contamination in downstream production processes.

It can also be used to reduce

It should be

noted - that the solvent cleaning process is a significant source

of chlorinated solvent emission and hazardous waste generation.

- Solvent cleaning can be classified into two major

categories: cold cleaning and vapor degreasing.

- Cold cleaning is used to remove drawing compounds,

cutting and grinding fluids, polishing and buffing compounds and

miscellaneous contaminants such as metal chips.

techniques include wiping, dipping, spraying, soaking, swabbing,

hersing, brushing and ultrasonic agitation. Cold cleaners are

the simplest type of cleaner, In some cases, blends of solvents

such as chlorinated solvents and alcohols may be considered for

cold cleaning applications.

Cold cleaning

- 3 - A4

The vapor degreasing differs from cold cleaning in that

it is normally conducted at the boiling temperature of the

solvent. In general, a vapor degreaser is a steel tank with a

stream or electrical heating coil below the liquid level and a

water jacketed vapor cooling and condensing zone above the vapor

level.

solvent vapors rise inside the tank to the level of the primary

condensing coils.

workload as it enters the vapor zone and dissolves and removes

the contaminants.

reaches that of the vapor, condensation ceases and cleaning is

completed.

The work piece is placed in the vapor zone. Boiling

Solvent vapors condense on the cooler

When the surface temperature of the object

Impurities accumulate in the boiling sump below.

- Dry Cleaning Industry

Dry cleaning is similar to the common laundering

process.

instead of detergents and water. In general, all kinds of

textiles including both natural and synthetic fibers can be dry

cleaned, provided they are resistant to the dry cleaning

solvents and the frictional activity involved in dry cleaning

washers .

The major difference is the use of chlorinated solvent

I

I

.

- 4 - A5

There are three principle steps in dry cleaning c

operations: cleaning or washing, extracting, and drying.

Cleaning steps involve washing of garments, extracting used

solvent for recycling and 19drying9’ the solvent, which means

separating water from the solvent’. The dry cleaning washer

serves as an extractor by causing the wash wheel to whirl at

high speeds. The freed solvent is then cQllected and stored for

reuse .

Extraction is essential to any dry cleaning operation.

It reduces solvent losses, eliminates wasting and dripping of

solvents, and reduces the weight of wet garments. The drying

process removes any solvent remaining in the garments by

~ tumbling them in a stream of warm air.’ A properly functioning

dryer can remove between 85 to 95 percent of the solvent2.

When the removal of solvent is complete, the clothes are treated -

with a stream of fresh air, a process called deodorizing or

aeration.

SOURCE RE3UCTION OPTIONS

In what follows, a substitution analysis of chlorinated

solvents in cleaning operations is presented. This is limited

to the technical suitability dimension. Other dimensions, such

as cost and health effects are beyond the scope of this

- 5 - A6

analysis.

substitutes, will specify the contaminants that can be removed

The following sections will discuss the available .. and the characteristics that the alternative solvents must

possess to meet reasonable standards in cleaning.

In principle, an ideal substitution would consider all

possible substitutes and compare them along three dimensions.

The first dimension is technical suitability. All candidates - should be compared in terms of their capability to accomplish a

m

. specific task. The second is economic. The complete cost

analysis of a substitlute includes the cost of raw material,

associated equipment, process changes, regulatory requirements

and disposal. The third dimension is health implications. The

possible consequences of producing, using, and disposing of each

candidate. Human health impacts based on toxicological data for

-

each substance would alsdbe necessary, In this paper, we focus

on the first dimension, the technical suit-Xbility.

A summary of the source reduction options to replace

the chlorinated solvents in the two sectors is presented in

Tables 1 and 2.

substitution measures are considered, and the drawback and

advantages related to each option is summarized.

information on the individual source reduction options, the

reader is referred to references 1 and 2.

In the tables., only the chemical and process

I'or further

A7

The effects of substitution are complex and can be c

unexpected since possible alternatives to a hazardous chemical

may themselves be hazardous but in a different way, and there

may be no valid way to compare them.

As Tables 1 and 2 summarize, there are a variety of

source reduction options to replace chlorinated solvents in the

solvent cleaning and dry cleaning industries.

the various options themselves may have adverse features which

would not allow for complete replacement of the chlorinated

In some cases,

solvents in all sectors.

Options in Solvent Cleaninp -

In cleaning applications, there are a number of - chemicals that are technically feasible substitutes for both

cold cleaning and vapor degreasing applications%. -

Low molecular weight solvents such as aliphatic,

aromatic and oxygenated solvents are possible chemical

substitutes for chlorinated solvents. Most of these solvents

show good solvency charactecistics, however, they have several

limitations such as low vapor pressure, flammability and are

considered precursors to photochemical smog.

A8 - 7 -

Table 1

Source Reduction Options for Chlorinated Solvents in Cleaning Applications

Source Reduction Option

Chemical Substitution Advantages

o Low Molecular Weight o Good cleaners of of oil and grease, compatible with metals

Organic Solvents

o High Molecular Weight o Good cleaners of Organic Solvents oils and greases, noncorrosive

. o Good solvents, stable, low ozone depletion, non VOC

o HCFCs and Solvent Blends

Process Substitution

0 Aqueous Cleaning. o Removes salts and particulates

o Emulsion Cleaning o remove oil, greases and waxes

Drawbacks

o VOC, flammable, high vapor pressure

o Combustible, VOC slow drying, pretreatment required, toxic

o No toxicity data, not available for 4 years

o Low solubility of organic soils, slow evaporation, rusting , pretreatment required

o Leaves oily residues, disposal problems

Table 2

Source Reduction Options in the Dry Cleaning Industry

Option

Chemical Substitution

o TCA

0

0

- 0

CFC-113

Petroleum Solvents (Stoddard and 140°F Solvent )

CFC-123 and CFC-141b

Process Substitution

o Laundering

Advantases

o Non VOC, higher TLV, nontoxic

o gentle solvent. safe to use

0

0

Good solvency, higher TLV

Good solvent power, non VOC

o No solvent is required

Drawbacks

o Toa strong a solvent, ozone deple tcr , stainlcsg steel equipment required

o ozone depleter, expensive, not suited for all cleaning

o VOC, f lanmable, explosion-proof equipment required

o Low ozone depletion, low boiling point

o Not suitable for all fabric, special finishes required, increase sewer loading

- 9 - A10

They may be used to clean surfaces r with typical

contaminants susceptible to solvent removal including most

greases, oils, waxes, resins, and polymers. These chemicals are

presently used as simple substitutes for halogenated solvents in

cold cleaning applications.

required, the solvents show high solvency for common

-

~

~

No major equipment modification is

contaminants and chemical cotllpatibility with all ferrous and

1 nonferrous metalsa.

Orgafiic solvents have several limitations. They cannot

be used in enclosed systems because of solvent vapor build up.

These solvents can not be used in vapor degreasing applications

because of their flanundbility.

solvents is that they have short atmospheric lifetimes and they

form precursors that contribute to photochemical smog.

Another disadvantage of these

- -

High molecular weight organic solvents such as

terpenes, N-methyl pyrrolidene (NMP) and dibasic esters (DBE)

are very new to the solvent cleaning market and are not widely

used. These chemicals are considered biodegradable substances

by their manufacturers and are rated combustible due to their

flash point by the National Fire Protection Association. The

flash point of Bioact DG-1 (a terpene product marketed by

Petroferm, Inc.) is 47OC (117OF). These substances because of

their combustible nature should be used at room temperature.

-

A 1 1 - 10 -

Furthermore, a terpene supplier contends that the parts need to

be washed with water afterwards to remove the terpene residue,

which are too heavy to volatilize. This in itself may pose some

problems since the stream may have to be handled properly (i.e.

pretreated) prior to sewer discharge. To overcome the

flammability problem, nitrogen inerting systems are proposed

which will add tG the expense of the unit. It should be noted

that at this time, not much is known about the toxicity of these

chemicals and it is not clear if they can be recycled for reuse.

.

The new CFC'that is under investigation as a - replacement for CFC-113 and other chlorinated solvsnts is

CFC-123, which has shown good solvent power, stability, low

surface tension, and low ozone depletion potential, because it

contains hydrogen. CFC-123 has a low boiling point (27.7OC)

which is advahtageous for some applications such as cold

cleaning but disadvantageous for others. A consortium of CFC

producers has organized a toxicity testing program to test the

chemical for chronic toxicity effects. New CFCs would not be

commercially available for the next five years.

Some other solvent blends such as Freon SMT and ISC-108

are available as partial substitutes for chlorinated solvents

since they contain a small percentage of chlorinated solvents,

The Freon SMT which has been marketed by DuPont has 68 percent

. - 11 - A12

CFC-113, 25 percent 1,2 Dichloroethylene and 6 percent alcohol.

ISC-108 which has 0.4 percent TCA by weight in an alkaline

solution with a surfactant, is considered a biodegradable

compound and reqrtires neutralization prior to discharge to the

sewer .

A number of processes are available and are potential

for chlorinated solvent - degreasing. Aqueous cleaning is popular

for removing contaminants from various media.

The water based cleaning methods usually employ simple

hot water with some additives in combination with mechanical,

electrical or ultrasonic energy. Aqueops cold cleaning is

popular for removing contaminants from metal furniture,

fabricated product, and transportation equipment.

Water, although it may be used in a variety of

different industries, can not be substituted for cleaning of

products where its use may induce material or substrate

corrosion.

water, parts with mall interstices may not be effectively

cleaned. AqueouS cleaning can remove potentially damaging

chloride residues in industrhl soils that can not be removed by

vapor degreasingl.

replace solvent applications is not known; complete substituticn

At the same time, because of high surface tension of

The extent to which aqueous cleaning can

.

- 12 - A13

is probably not possible and applicability needs to be

determined on a case by case basis.

Water has several disadvantages. It has a low

solubility for organic soils such as greases.

slowly, it conducts electricity, it has high surface tension and

it causes rusting of ferrous metals and staining of nonferrous

metals. Aqueous cleaning is likely to leave residual water on

cleaned parts which can promote corrosion. Manufacturers of

aqueous systems sometime& recommend the use of a final rinse

with rinse inhibitor to resolve this problem.

can be achieved using a hot air knife, soak tank or rotary drum

It evaporates

Drying of parts -

washersa. - .

Also, water which is a nonhazardous material becomes

hazardous when used and requires appropriate handling such as

pretreatment prior to discharge to the sewer.

pretreatment costs, present equipments need to also be modified

for use of the aqueous cleaning process.

In spite of the

Emulsion cleaning is another possible substitute for

chlorinated solvent cleaning applications.

primarily used in the process of cleaning metal parts to remove

pigments or impediment drawing compounds, lubricants, cutting

fluids and metal chips.

Emulsion cleaning is

'Emulsion is not a substitute for vapor

4

- 13 - A14

degreasing since it leaves a light film residue or r oil onto the

parts.

maintenance and repair operations that require parts without oil

or residue.

cleaners is necessary.

This film may be good for rust protection or bad for

Sometimes subsequent cleaning with alkaline

Options in Dry Cleaning IndustrY

There are a number of chemical and process substitution 9

measures that can be applicable in the dry cleaning industry.

These - are explained below.

TCA, like PERC, is a chlorinated hydrocarbon but it is

a more aggressive cleaner and i t can 'attack plastics and dye.

Dow Chemical is presently examining TCA as a PERC substitute

largely because PERC is undergoing intense regulatory scrutiny.

Presently, only about 50 dry cleaners nationwide or about 1

percent of dry cleaners use TCA.

associated with TCA is that it is an unstable compound that

readily decomposes to generate acidic by-products.

need to 3e added to the chemical to prevent decomposition.

also requires expensive stainless steel equipment to withstand

acidic environments.

.

The problem generally

Stabilizers

TCA

Control and recovery of TCA on-site by

vapor refrigeration or carbon adsorption mzy remove the

stabilizer from TCA. It could be damgerous for generators to

I

- 14 - .

reformulate the solvent because the stabilizers are frequently

toxic or explosive. TCA is also a more expensive solvent than

PERC, and has been pragosed by EPA to be regulated domestically

as a stratospheric depleter.

this solvent in the future.

Y

This would limit expande2 use of

CFC-112 is presently used in less than 2 to 4 percent

of the dry cleaning'.

cleaner than PERC and it requires a specific type of

conservative equipment because of its expense.

presently used as a &y cleaning solvent because of its light

soil cleaning power, low toxicity, stability, nonflammability,

and relatively low boiling point.

enclosed dry-to-dry machines, which incorporate solvent recovery

systems (refrigeration, filteration, and distillation). A

typical CFC-113 machine clGans more than SO kilograms of

clothing per liter of solvent consumed.

CFC-113 production will be capped at 1986 levels in the near

future and will be reduced to SO percent of 1986 production

This compound is a less aggressive -

CFC-113 is

-

CFC-113 is used in totally

*

Asmentioned earlier,

level in 1998.

is probably going to be off the'market in 10 years.

What this means to a dry cleaner is that CFC-113

- These solvents (also called Stddard solvents) possess

. characteristics that make them potential substitutes for PERC

and they are used by 20 percent of dry cleaners today. If

- 15 - .

petroleum solvents are to be used instead of PERC, however, the

cleaning must be done in explosion proof machines.

solvent has a flash point of 103OF.

major pieces of existing PERC systems be replaced.

believed that it would be hard to find Stoddard equipment.

c

The Stoddard

This would require that

It is also

- Although conversion of equipment is certainly

technically possible, local fire codes nay require extensive

remodeling of the building where petroleum solvents are used;

indeed, in some cases, this conversion may not even be allowed.

Conversions may be less feasible in an existing plant than in a

new dry cleaning plant where the required features could be

designed in from the outset. Other conditions under which - conversion may not be feasible are:

leasing a space where extecsive changes to the building may not

be allowed; if fire codes prevent the use of petroleum solvents

(Class 11); if there is an adjoining occupancy; or if the city's

ordinances preclude the use of petroleum solvents in parts or

the entire city.

I

! I

if the dry cleaner is .'

Petroleum solvents have cleaning ability similar to

PERC and do not' damage articles.

(leather, for instance), petroleum solvents are preferred to

In fict, in some applications

- 16 - 83

PERC because they cause less daage to the garments. The same

rate of cleaning can be accomplished with PERC in a dry-to-dry

machine and petroleum solvents in transfer machines.

The toxicology of Stoddard solvent is an unresolved

issue. The emission of hydrocarbon solvents into the atmosphere

is currently regulated as a precursor to shotochemical smog.

EPA has strictly regulated 2mission levels at 500 ppm. Also,

since petroleum users often store the solvent in tanks, they are

subject to federal regulations on storage tanks. .I

- A small amount of dry cleaning is carried out with

140°F solvent, so named because its flash point is 138.2OF (or

6OOC).

specifications similar to those of Stoddard solvent, except for

the distillation range, which corresponds to the temperature

range of the upper half of Stoddard solvent. When used with

special equipment, 140°F solvent may be employed in many

locations where fire restrictions would prohibit the use of

Stoddard solvent’. It is, however, more expensive and has a

longer drying time than Stoddard solvent.

The solvent is a petroleum distillate with

-

-

- 17 84

A n u m b e r of EFCs and HCFCs currently are under

development and are likely to be available commercially in the

next five years. Possible substitutes includes HCFC-14lb and

HCFC-12' . The properties of HCFC-123 and HCFC-14lb a- re summarized

- in Table 3. HCFC-123 seems to be a candidate - for use in the dry

cleaning industry, although presently no testing has been

performed on the suitability of this solvent.

CFC producers has organized a toxicity program to test the

chkical for chronic toxicity effects. W o n t has recently

announced that it will build the first large scale HCFC-123

A consortium of

- * plant in Maitland, Ontario.

HCFC-123 has a very low ozone depletion potential

because it contains hydrogen, it has low photochemical

reactivity, good solvent power and stability, and low surface

tension.

solvent needs to be used in leak proof equipment.

equipment modification to allow use of HCFC-123 in existing

ECFC-123 has a low boiling point which means that the

The extent of

equipment is not known. -

EPA is currently considering a restriction or ban on

TCA because it contributes to ozone depletion potential.

HCFC-123 has an ozone depletion potential only about 0.02 which

65 Table 3

Chemic&, Characteristics of -2lected Solvents

Heat Required Ozone'

Solvents Molecular Flammability Boiling Point One Gallon' Butanol Depletion to Boil Kauri

Weight ('(2) (BTU) Value Potential

CFC-113 187. S

Perchloroethylene 166 Stoddard -

b NF

NF

F C

F 140-F - TCA 133.5 NF

HFC-141b 116.9 F

HFC-123 153.0 NF

47.6 (118.F) 1,160 31

121.1 I250-F) 2,090 92

154.4 (310-F) 7 32-36 d

d 185 (365.F) ? 34-59

75 (167-F) 1,630 124 d

d 32 ( 89.6.F) 7 ?

28.7 ( 83.66-F) ? 3

.02

-1

-.l

* 02

a Heat ;.?@red to boil one gal1:an of solvent from 20.C.

NF - Nonflammable. F - Flammable.

* Need Information - compared to CFC-11 with value of 1.0 and estimates based on preliminary incomplete data except f o r

SOURCE:

CFC-113 and TCA.

Source Reduction Research Partnership (SRRP), "Solvent Cleaning Industry Profile - Draft", October 1989. I

- 19 -

is much less than TCAs ozone depletion potential c about 0.1.

may ultimately regulate other minor contributors to ozone

depletion if they achieve widespread use. The regulatory future

of HCFC-123, like other new HCFCs is therefore in questions even

before any of them have been produced.

EPA

Although HCFC-123 holds prcmise as a substitute dry

cleaning agent, it probably will not be available for another

three to four years until animal testing is complete.

is expected to be much more expensive than PERC.

HCFC-123

In spite of

all . these, HCFC-123 may be used in new tighter equipment which reduce solvent use dramatically.

HCFC-14lb (l,l,-dichlor6-1-fluoroethane), like HCFC-123

is not a fully halogenated CFC, although it contains chlorine.

HCFC-141b has an atmospheric life that is comparable to TCA.

This could mean that EPA may eventually regulate this chemical

as a stratospheric ozone depleter. Like HCFC-123, HCFC-141b hac

L

been exempted as a photochemical smog contributor by EPA.

indicated in Table 3, the boiling point is lower than PERC,

which means that it needs to be used in tight equipment.

also suggests-that roughly 50 percent more HCFC-14lb or HCFC-123

needs to be used to clean the same amount of clothing.

A s

This

67 - 20 -

Some major drawbacks of HCFC-l4lb are that it is

flammable, and is somewhat toxic. Flammability can cause

workplace problems and would increase the cost for building

modifications. HCFC-141b has also been found to be a weak

mutagen in short-term tests; the CFC producers are now

sponsoring chronic tests on the chemical and the results would

not be pailable until 1993.

r

There is an existing commercial production process for

HCFC-141b which allows coproduction with HCFC-142b using TCA as

a chemical intermediate.

would not be initiated unless the lifetime animal studies show

The commercial production of HCFC-141b -

no toxicity problems. -

HCFC-123 seems to be a preferable solvent in the dry - cleaning industry.

problems of HCFC-l4lb, although it fs cheaper, and less of it

need to be used. As was pointed out, HCFC-123, needs to be used

This is partly due to the flammability

in tight equipment.

International Fabricare Institute (IFI) has performed

some initial testing of HCFC-lllb in existing fluorocarbon

equipment.

according to one source HCFC-141b solvent power was quite

attractive.

The results af the test is confidential, but

The major problem with HCFC-141b is its

88

1'-

flammability problem.

been introduced which could overcome the flammability issue but

the boiling point of the mixture would be lower than HCFC-lllb,

abeut 81 to 89O F, which could mean a substantial amount of

solvent can be lost to the atmosphere, since the boiling point

is at room temperature.

point of about 40" C.

In fact, a HCFC-141b and HCFC-123 have

An ideal solvent should have a boiling

Laundering is a process alternative to dry cleaning.

During laundering, soils and stains are removed from textiles in

an - aqueous medium. Laundering can be considered a substitute for dry cleaning only when the textiles can be c, 3 eaned with

water without any damage. The process is commonly performed in

home washing machines and it can be used to handle natural (for

instance, cotton) or synthetic fibers (for instance, nylon,

polyester, and their blends).

and siiicated alkalies are usually used, as opposed to

detergents and soaps in home laundering.

In commercial laundering, caustic

The major shortcoming of laundering is that many

fabrics such as wools can not be cleaned using an aqueous

medium, unless they are handled differently. Wool can be treated with finishes that permit laundering of the material

without shrinkage.

laundering of more and more garments.

Future developments may allow increased

- 22 - B9

CONCLUSION

For years, traditional end-of-pipe pollution controls

have shifted attention away from pollution prevention measures

toward compliance with a set of expensive, frequently

inconsistent regulations, which promote end-of-pipe pollution

control in a media-specific manner. The regulatory regime that

has evolved does not promote a systems approach in the use and

management of toxic chemicals. Today, however, pollution

prevention makes environmental sense and is, in the long run,

prqfitable to industry. Pollutants that are not produced in the

first place will not harm human health and the environment or

require future cleanup expenditures.

However, pushing users from one chemical to a new one

that has not been adequately scrutinized and whose consequences

are unknown must be avoided. The real questions are how to

safely eliminate or reduce the use of hazardous substances in

commerce . Toward this end, waste-reduction opportunities need to

be communicated to many chemical users in a responsible manner

to allow users to make informed choices from among the many

source-reduction options.

B10 - 23 - References

1. Source Reduction Research Partnership (SRRP), "Solvent Cleaning Industry Profile - Draft", October 1989.'

2. SRRP, ''Dry Cleaning Industry Profile - Draft", October 1989.

e

&p lndustry and Environment January/February/March 1988 Page 29

controls, wherein some highly ike polychlorinated biphenyls entry into the country.

In Thailand, techniques such as trade effluent standards, environmental impact assessments, and tax incentives arc used to reduce b e generation of hazardous wastes.

Conclusion

In the overall framework of environmental protection in the ASEAN region, greater awareness for the protection of the environment should be encouraged. Although it may be difficult to achieve in practice, dialogue and good relations must be cultivated between government and businesdindustry groups who will have to respond to enforcement measures or even to anticipate them. For the development of a comprehensive system of disposal of hazardous waste, the following must be taken into account: 1) existing laws and regulations that have a bearing on the subject must be assessed; 2) provisions on criminal and civil liability for the improper disposal of hazardous waste must be regarded only as a support measure; 3) the authority responsible for prosecution might need to be informed and educated, since offences under Environmental Protection Law are still often regarded as “gentlemen’s offences”; 4) cen- tralization with a specialized and specifically trained prosecution authority is an effective means of improving enforcement and should therefore be considered; and 5) civil liability should provide for damages as a result of illegal hazardous waste management. Re- sponsibility will therefore be based on the principle of forts, which requires the plaintiff to prove negligence.

To be effective, management must be en- forced, and necessarily, it must be multi-dis- ciplinary. It therefore demands expertise in many fields. It should be the long-term objective of developing countries to establish technical, legislative and administrative measures. However considerable time will be required to achieve such objectives.

References

Danusaputro, M. “Environmental Legislation and Administration in Indonesia”, Alumni Press, Bandung 1980. Lam, M.P. “Country (Malaysia) Monograph on

Institutional and Legislarive Frameworks on En- vironment”, Bangkok, 1983.

Liew, W.Y. “Country (Singapore) Monograph on Institutional and Legislative Framework on En- vironment, UNIESCAP”, Bangkok, 1983.

Panat, T. “Country (Thailand) Monograph on Institutional and Legislative Framework on En- vironment”, Bangkok, 1983.

Results of the ASEANNNEPICDC Workshop on Guidelines for Establishing Policies and Strategies for Hazardous Waste Management in &a and the Pacific, Singapore, 1986.

Seriga, P., Passe, S., Leido, 2. “Management of Toxic Chemicals and Hazardous Substances”, Philippine Environmental Law, vol. 11, National

1 Environmenrd Prorcction Council, Quczon City,

Joanna D. Underwood, ElMtlVC DIrmor, INFORM, 381 Park Avuruc South, New York, NY 10016, USA

Nearly everyone today agrees that hazardous chemical wastes are a serious threat to human health and the environment. Since the debut of the chemical industry in the 1 9 4 0 ~ ~ the production of chemicals has burgeoned to hundreds of billions of pounds a year. And in the wake of producing a multitude of products ranging from plastics, to drugs, to solvents - a flood of toxic and hazardous byproducts has been generated contaminating our land, air and water.

Both govemments regulating the disposal of chemical wastes and industries producing them have focused on “managing” them - putting them in landfills, inanerating or otherwise treating them in order to control the pollution risks to people and the environment. But managing hazardous wastes to control pollution has proved to be an insufficient answer to the growing critical problems caused by such wastes.

The limits of pollution control

The shortcomings of “pollution controls” are numerous. Such controls may often just move hazardous pollutants from one environmental medium to another rather than getting rid of them. There arc air and water treatment technologies such as baghouses and scrubbers that produce hazardous waste dusts or sludges which must then be landfilled. There are evaporation ponds or air stripping columns used to treat liquid wastes that in their rum put some of the volatile chemicals in these wastes into the air. Then there are absorption materials used to remove toxic matter from liquid wastes or gases. These absorption materials are then sent to landfills where they create a potential groundwater contamination problem.

Hazardous waste reduction: the number one choice The best answer to the industrial hazardous waste problem is to reduce those wastes at their source; i.e. to prevent their production. This reduces the generation of wastes discharged to all environmental media (air, land and water) and protects both the health of the citizenry at large and the health of industrial workers who are exposed at their worksites to

. . ,

More than a deade ago, the U.S. Environ- mental Protection Agency articulated a preferred hierarch? of waste management practices. At the top of the hierarchy - as the first option to pursue whenever possible - was waste reduaion. The second altema- tive was recycling for wastes that cannot be prevented, industrr should find ways to reuse them. The third choice was treatment; the wastes that r e m a k d despite the best efforts to prevent or r g c l e should be destroyed through efiectivc treatment operations. Dis- posal in pits, lagoons, deep wells and at sea was classified as the least desirable method of dealing with wastes. This hierarchy of hazardous waste managc-

ment options has now been endorsed widely in the U.S. by groups ranging from the Congressional Office of Technology Assess- ment (the research arm of Congress) to the Chemical Manufimurers’ Association. The primary importane of waste prevention has now also been enunciated as a key goal for the European Comunities in the Third En- vironmental Actioc Programme.

So today, waste reduction is widely accepted, in theoF. as the best possible solution. Yet the strategy still seems to be receiving very little actual attention. In the U.S. this has certainly tven the case. Research that INFORM has conducted (which will be discussed later in & article) and research by the Congressional Office of Technology As- sessment, have concluded that both U.S. Go- vemment and industry generally continue to place their primvy emphasis on pollution control and treatment options: “end-of-the- pipe” methods gcved to cope with already created wastes. They seldom look first for ways to reduce or prevent wastes.

~

The threat of toric waste

Unless the huge output of hazardous waste is reduced at source, mankind can expect little real improvement in the critical risks affecting the world environment and human life. In the U.S. alone, the chemical industry has a total production that !.xis skyrocketed in just 40 years from 20 to over 220 billion pounds a year. More than 70 000 chemicals are now in commercial u x with 500 to 1000 new ones

-

- A d d ~wn-. I---- q-4 from F h k rhPm;.-nl in.

4

Page 30 UNEP Industry and Environment January/February/March 1%

dustry activity roughly 583 million pounds of solid hazardous wastes a year are produced, nlus millions more of those wastes that are re-

,‘he U.S. has now over 20000 hazardous waste sites to contend with (950 on its list of critical “superhnd” sites posing an immediate threat to public health). There are probably at least another 200 000 “unofficial”

~ pits, ponds, and lagoons across the countryside containing wastes suspected of containing hazardous materials. All these wastes represent an increasingly ominous liability, jeopardizing both public health and our natural resources.

The possible adverse effects of these chemicals vary greatly. Some are potentially lethal. Others are implicated in gene mutations, birth defects, reproductive failures, or nerve damage. Only a small fraction of the 70 000 commercial chemicals have been subject to a level of toxicological testing that could determine their long term impact on public health. A 1984 study by the National Re- search Council in fact concluded that in the U.S. there is insufficient information for even a partial health assessment for roughly 90 per cent of them. Such data is certainly no better in Europe. Largely as a result of limited health effects data, the U.S. (whose regulations of chemicals are mainly based on iden- ;Gable safe levels of urposure) has been able

set specific regulations for relatively few substances: just over 600 discharged in solid form, 126 as “priority” water pollutants, and less than a dozen chemical categories as air pollutants.

cd to the air and waterways.

&

The largely untapped potential of waste reduction

In 1986 INFORM published a 550-page srudy, Cutting Chemical Waszes, on the waste management practices of 29 of the over lo00 U.S. organic chemical plants. The research documented 44 initiatives taken to reduce wastes - initiatives suggesting the great potential of the waste reduction strategy. Some of the initiatives taken by INFORM’S study plants reduced hazardous waste streams by 50 per cent, 80 per cent, or more. Plant waste

I reduction practices involved five different i kinds of changes: 1) process changes, such as ; altering reaction temperatures; 2) changes in I plant equipment; 3) reformulating products;

4) substituting harmless chemicals for toxic ones; and 5) simple operating and housekeep ing changes.

At the same time as these waste reduction , changes reduced companies’ human health and environmental liabilities, many also improved plant economic efficiency. For example, one of the plants that INFORM studied (a New Jersey facility operated by =ON) achieved a 90 per cent reduction in

from its chemical storage by ~ P I Y installing “floating roofs’’ on

-290 1- mnuining the most vo- of Ihac roofs resulted

Another plant studied - a resin-making operation owned by Borden in California - achieved a 93 per cent reduction in its phenol waste stream which had, for over two dc- cades, been channelled to a local sewage treatment plant. Borden did this by making a series of quite simple, straightforward, plant operational changes. In addition to changes in procedures for rinsing plant filters, and handling of the hoses used to move chemicals from one tank to another, a major step involved altering procedures for rinsing out chemical mixing vats. By convening from one- to two- stage rinsing, concentrated chemical wastes could be collected for reuse in the first rinse, and only the diluted second rinse wastes b e came part of the waste stream. Borden saved hundreds of thousands of dollars in reducing raw material losses and its pollution control costs.

While MFORM’S research found a- citing particular examples of waste reduction, it also documented how limited the overall level of plant initiatives were. It was most often that waste reduction was turned to as a viable strategy only in cases where available treatment and disposal strategies failed. The result was that waste reduction initiatives at all 29 c a s study plants were a f k b g less than one per cent of the billions of pounds of total wastes discharged. (A new round of IN- FORM research this winter will re-visit the same 29 plants to define what progress may have occurred in the last 18 months.)

Two major U.S. government studies, published in 1986, acknowledged the limited attention paid to waste reduction so far in this country but estimated that significant amounts of waste reduction would be readily achievable. Their estimates seem eminently reasonable in light of INFORM’S chemical plant case study findings. One study, published by the Congressional Ofice of Techno- logy Assessment, predicted that a 50 per cent reduction of all hazardous wastes in the U.S. could be accomplished by industry over a five-year period. OTA’s report, entitled Serious R h w n of Hazardour Wastes, both argued for the primacy of waste reduction among waste management strategies and concluded that for every dollar spent by U.S. business and government on waste reduction, $50 could be saved. Another 1986 report published by the U.S. EPA projected more conservatively that over the n u t 25 years up to 30 per cent of hazardous wastes could be reduced.

Obstacles to progress Despite the potential advantages of hazardous waste reduction and the urgent need for use of this strategy, waste reduction still occupies a second-class position in practice in the U.S. because of a variety of obstacles. A major ob- stacle lies in the continuing government policies favouring pollution control mentioned earlier. Not only are waste treatment and disposal still the primary focus, but in the U.S.

.. . . .

-

the most attention. These only aim at r&c- ing solid landf~lled wastes. Government has put a lower priority on reducing air and water pollution produced by plants.

INFORM’s study, which also examined the chemical uses and discharges of each of the 29 plants, revealed why the emphasis of U.S. policy makers on preventing landfilled wastes rather than on preventing all types of wastes at source has been misplaced. Analyses of the discharges of eight organic chemicals from INFORM’s study of plants in New Jersey revealed that while 35 per cent of chemical wastes were generated as solid wastes, 23 per cent were air pollutants, and 42 per cent were water pollutants. Wastes to all environmental media clearly merit equal attention.

The U.S. Government has also discouraged an intensive corporate search for waste reduction opportunities by allowing industry to continue to use inexpensive waste disposal alternatives. As long as companies have access to landfills, deep wells, and sewage treatment plants to dispose of their wastes, there is little incentive to look in new directions. It is no surprise that in the U.S. most of the hazardous waste generated gocs into the least expensive disposal route: deep well injection. Over 195 deep wells are in operation today.

Other obstacles to hazardous waste reduction exist in industry. INFORM research documented the fact that chemical company oflicials, like the environmental regulators dealing with them, were preoccupied with reacting to existing hazardous waste problems, and their reactions were mainly focused on end-of-thc-pipe responses. &on installed the floating roofs on its chemical tanks - which proved to be such a simple and economical move - only after the State of New Jersey required this change. Borden, likewise, sought ways to reduce its phenol wastes when the local sewage treatment plant was no longer willing to accept them. U.S. corporate managers have delegated

waste problems to those whose expertise is in use of traditional pollution controls and who have little authority over (or expertise with) the plant processes that generate the wastes. Waste reduction progress requires a “top down approach” and the direct involvement of corporate management and of plant operat. ing managers rather than primarily the in wlvcment of plant engineers responsible fol environmental or regulatory compliana whose training is in handling wastes a l r e a d r generated.

At most of the plants INFORM studied neither corporate nor plant managers had in formation systems telling them which waste- were coming from which production prc cesses nor accounting systems to help defin the costs of wastes from each plant operatior In short, the reasons for ignoring waste redw tion initiatives by industry in the U.S. we: found to be largely institutional, not the rl sult of technical, legal or economic cot straints.

The price of continuing to focus on poll)

-

-

-

. - - - - . - , . I . . I..-

*, uNEP Industry and Environment JanuarylFebruarylMarch 1988 Page 3 1

- ~ ~ J 9 9 0 , up to 56 000 companies producing

wastes in the U.S. will be rquired the Environmental Protection Agency to dumping their billions of pounds of solid

mpstes a year into landfills - an important wvcmmental move geared to foreclose one heretofore cheap waste disposd alternative. If the current focus of industrial practice on pollution controls persists, most of the companies may well decide to invest in incine- fotors and other costly treatment methods to rid themselves of these toxic wastes. Un- fortunately, in many cases these alternatives will both be atremely expensive (incineration can cost 15 to 150 times as much as land- filing) and less satisfactory from the perspective of environmental protection, inevitably shifting much of the polluting material from land into the air or local waterways.

@

What government and industry can do

The problem of hazardous waste reduction, therefore, comes down to solving the problem of changing both govemment and industry priorities for dealing with such wastes. In the U.S., INFORM, on the basis of its research, identified steps that state governments could take to promote hazardous waste reduction. These steps, discussed in some detail in a new INFORM paper, entitled Promoting Ha- zardous Waste Reduction: Six Steps Statu Can Tuk, include the following:

(1) Establish the accepted hierarchy of hazardous waste management practices - r e duction, recycling, destruction and disposal - as explicit government policy.

(2) Establish a State office with thrn distin- guishing characteristics: it should be at a high level; it must be headed by a r e spected official experienced in working with business leaders; it should be sep arate from other offices in the agency focused on the more reactive h c t i o n of regulating already generated hazardous wastes.

(3) Delegate key responsibilities to the office, ranging from setting waste reduction goals and reviewing rquired waste audits of plants to training personnel and sponsoring meetings to promote waste reduction.

(4) Establish state programmes involving technical and financial assistance and create information clearinghouses to stimulate voluntary hazardous waste reduction initiatives by industry,

(5) Take advantage of the requirements of government programmes regulating the discharge of specific chemicals to promote industrial hazardous waste reduction as the first response.

(6) Institute measures directly stimulating corporate action. These might include:

- require periodic preparation of waste audits and waste reduction plans by hazardous waste generators and reporting of the specific waste reduction initiatives taken and their results; making acceptance

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dition for approving permits which plants must obtain allowing them legally to discharge wastes.

- consider a comprehensive fee on hazardous wastes to directly promote source reduction. While a variety of fes, including fets on chemical feedstocks or on plant solid wastes, have been instituted by state governments to raise funds and deter wastes, none of these fees would produce this result. Only a comprehensive f n would provide a strong economic incentive to reduce wastes at source

- applied to all hazardous wastes generated, irrespective of the mnner in which they are handed or the medium - land, water or air - into which they arc discharged.

Because of the diversity and the dynamic nature of individual industrial waste generating facilities, INFORM concluded that regulatory prescriptions dictating particular technological approaches to be employed, or even levels of waste reduction to be achieved, would be inappropriate. As for changing U.S. industry’s attitude to-

ward waste reduction, this wil l probably d e pend on how strictly govunment acts in taking the kinds of steps INFORM has proposed, and also on how soon industrial management becomes awpn of the savings possible in hazardous waste reduction.

Over the last few years, some of the steps listed here to foster waste reduction have been taken by 10 to 15 states. North Carolina and Tennessce, for example, have established clearinghouses of information on waste reduction to aid industry, and have begun giving awards to outstanding firms and holding conferences to highlight this strategy. North Carolina and Minnesota are among states now providing technical help for companies. Min- nesota has a technology assessment programme called “TAPS’, providing graduate chemical engineering students as consultants to small and medium sued firms, which has been particuiarly visible. But no state has combined all the critical hazardous waste reduction state strategies in a well developed overall programme.

On the federal government level in the U.S. there are now three signs of progress:

1) a provision in the 1984 Amendments to the U.S. Resource Conservation and Re- covery Act (RCRA), requiring plants which are sending solid hazardous wastes to off-site disposal facilities to sign a statement indicating that they have taken steps to reduce these wastes. This, at least, requires them to focus on the question;

2) incorporation in our country’s federal waste site clean-up bill at the end of 1986 of a new requirement that the Environ- mental Protection Agency conduct the first extensive inventory of the annual use and discharge by industrial plants of 309 separate chemicals plus an additional 20 categories of other chemicals. This inventory, to be publicly available, will provide a base

r . r : . 9 I . . - -__--_. ^I-

cerned communities, and environmental ’

groups to track waste reduction results in fUture years; and

3) the introduction of the Hazardous Waste Reduction Act of 1987. This Act is the first significant legislation mpking mste reduction a major federal priority. It proposes on the federal level most of the steps that INFORM spelled out for individual states.

It is not clear to us at INFORM whether chemical and other hazardous waste producing facilities in the world, operating in different cultures and regulated under different laws, have sufiered from the same myopic concentration on pollution control as facilities in the U.S. Certainly industry and govemment leaders in every part of the world laud the waste reduction strategy with equal ar- dour. Independent government research of the practices of plants would be needed to tell how much waste prevention is in fact being practised. But it is clear that there i s urgent need everywhere to stem the continued out-

threats to our global environment. In any case, with the initiatives now taking

place in the U.S., the future of hazardous waste reduction in this country certainly seems to be more promisimp than it has ever been before.

pouring of toxic substances that pose severe

The publiccltionr r e f d to in this artk& are available from INFORM, 381 Pork Avenue South, New York NY 10016, USA.

Major technological accidents prevention

As a WICEM ‘follow-up, experts from industries or consulting firms in industrialized countries are willing to provide in 1988, on a case by case basis, free or low cost short-term expertise to help perform safety audits in a few industrial plants in industrial- izing countries. To know more about such a possibility and under what conditions, please write to UNEPflEO.

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i

HE PARETO PRINCIPLE IS several things. It is a state

Pareto charts l’ 0fnarure.rhewaythrngS happen around us. It is I also a way of managing

projects. F d y , it is a process-a

that a&ct us.

can help identify the few problems that cause

way of thinking about

stataatnablm The Pam0 principle was first the greatest

defined by Joseph Juran in 1950.’ During his early work. Juran found that then was a “maldistri- bution of quality losses.” Not lik- ing such a long name. he named the principle after V i 0 Rutto. a WIcentury Iuiian economist. hea~ found that a large share of the d t h vns owned by relatively fnv people-a maldismbution of wealth.

Juran found this was true in manv areas of life. including aual-

loss of profit.

by John 1. Burr

F I

i i Measures Hours Down Oollar Cost # Nonconforming 1

Time To Do Impact on !

Customer I - i 1 . 1

I I

Categories Causes. Products. Manufacturing Lines. Onerators

Administrative Areas, Eauipment. Cost Centers

ity n;chnologies. In 1975, hz published a ”c- tion of his use of Faxds name in an article called ‘The Non-hero Principle: Mea Culpa.”2 Nevertheless. the term “Pi” principle“ is here to stay.

In simplest terms, the Fareto principle sugestr that most e f k s come from relmvely fkv uuses. In quantitative terms. 80% of the problems come from 20% of the machines, raw materials. or operators. Also. 80% of the wealth is controlled

by 20% of the people. It is well-known that 80% of the funds contributed to charity come from - only 20% of the possible sources. F d y , 80% of scnp or rework quality costs come from 20% of the possible causes.

In the quality technologies. Juran calls the 20% of causes the “vital few.”’ He originally called the rest of the causes the *‘mvial many.“ How- ever. he and other quality professionals came to understand that there are no mvial problems on

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Occasionally data arc not available. The situaaon might come up. for example. when a group must d e h e a problem or look for a cause. With a process flow diagram and a cause-and-efh diagram visible and under- standable to the group, each member must identify what korshe &is are the most impomntuusesofthcprob Ian. This can be done in three ways:

1. Each person votes on the major categories in the

each person explain why he or she is voung for a particular category. Often. consensus can be quickly reached: otherwise. a Pareto diagnm of the votes should be made.

2. Each person has live votesand can place rhemany- where on the cause-andeffcct diagram. It is good to do this in conjunction with a break so that each person has time to come to the diagram to make the marks. By the way, a person could give all five wtes to one cause if he or she felt very strongly about it. A Pareto diagram of the results should be made.

3. Then is a nominal technique that is more h l w d and particularly usdtl when there is a large number of possible causes and a good deal of uncertainty d which is important. This technique requires a laqe supply of 3 by 5 cards. All membcrs get 10 canis (or five hshort- a lists ofcauses). They write each oftheir top 10 choics on separate cards. They then pick the most likcly cause. This catd gets a IO. Next hey pick the least likely cause and give it a 1. Then the next least Likely cause is selected, a 2. Then the next most likely cause, a 9. This process is repeated back and forth until all the causes an ranked. (It is easier to select the most and the least likely causes than to distinguish among the ones in the middle) The numbers axe then compiled for each cause and 2 F?mto d w is constructed. This same technique can be used giving each person 100 points to dumbute among the ranked cards. The same process of compil- ing is then used.

The Pam0 principle describes the way cilllses occur in naam and human behavior. It can be a very power-

cause-and*ffi diagram. It might also be helpful to have

A

Product Problem

2 1 8 ' 10

Labels Liner Glue Score Warp

F G

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ful management tool for focusing personnel's efbn on the problems and solutions that have the p e s t potential payback. Rsbr&lesr

Others,'' I n d " b f Quality Con". October 1950. p. 5.

mss. May 1975. p. S

1. Joseph M. Jum. "Rueto, Lorem, Cournot. Bemoulli. Jumn and

2. Joscph M. Juran. 'Then and Now in Quality Control." Quafiry Rug-

3. Joseph M. Juran. editor, Qwf~iy Con" Handbook. 4th edition.

4. Joseph M. Juran. J u m on P m g j b r Quoriry (New York: The Free

5. Joseph M. Juran. Jumn on Leadcrshipjhr Q d i p (New Yorlc: The

6 J&ry Kalin. Rwenmion to the Rochester Section, ASQC. on Sep-

.

M d j w - H i l l Book CO., 1989.

Press. 1988).

Frre Press. 1989).

ormber6 1984.

John T. Burr is the founder of Rochester Quaiity Associates. Rochester. NY, and an assistant professor at the Center for Quality and Applied Statis- tics RDchestcr hr i tuoe of Tahnology. He holds a PhD lium Purdue Univer- sity. A Fellow of ASQC, Burr is a cenified quality engineer.

I

Recycle your plastic Source reduction and recycling are increasingly attractive altematives for HPI companies. A worldwide effort is already underway

UI! C. Kuhlke, DeWitt & Co., Inc., Houston, Texas

SOURCE REDUCTIOh' and recycling are alternatives to managing waste. This includes the recycling of material before it leaves the manufacturer or reducing the size of the product bcing niadc. In-plant reprocessing of plastic materials is one method of source reduction. Included are such applications as where an injection molder collects the spur, regrinds it, and feeds it back to make an injection molded part. When a polystyrene sheet is thermoformed to make cups, after cutting, the remaining sheet is recycled, chopped up and reextruded to make a sheet to again be fed to the thermoformer. The alternative would be to sell the waste or send it to the city dump.

An HPI application. Another good example of waste recovery is Mobil's purchase of film scrap from various polyethylene film producers. Mobil chops it up, adds a colorant to mask any contaminations and reextrudes it as trash bags. This procedure now represents over 100 million pounds per year. Other trash bag manufacturers have similar programs. It has been. and still is. economically justified to handle plastics in this manner.

Source reduction also means less material to begin with- lighter bottles. thinner walls whenever possible on injection molded items and thinner gauge films. Here the use of linear low density or high molecular weight films versus conventional LDPE (or for that matter, paper) to make grocery bags will be important.

Another example of source reduction would be to reduce the size of the package for compact disks to just the size of the C.D. rather than twice the size.

Recycling. The second way of reducing the amount of materials going into the waste stream is recycling. For plastics, this means the development of a new industry. To achieve this goal, the plastics industry is mobilizing to solve the problem. Plastic industries around the world are gearing up to accomplish this task. In the U.S., the Council for Solid Waste Solutions has been formed. In Western Europe, it is The Plastics Ll'aste Management Institute. In Canada, it is The Environmental and Plastics Institute of Canada, and so on.

To achieve these recycling goals, some major obstacles need to be overcome. How is the raw material collected? Does the consumer separate the garbage into glass bottles, aluminum cans, plastic bottles, newspaper and "all other" at the curb? If so, do the garbage trucks come around five times or do they have five compartments to contain the separated garbage? The waste disposal industry is looking at the alternatives. What other methods can be used to collect plastics from

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grade 2 0 1 1 1 I 1 1 1 1 1 1 1 1 1 1

1981 '82 '83 '84 '85 'e6 '87 '88 '89

Year by quarter

Fig. 1- Cost of recycling vs. virgin resin prices.

the consumer? Do we put bins at the entrance to stores to collect bags used to take home yesterday's goods?

Collecting used plastics and recycling them costs money. Table 1 shows the costs of recycling. Note: There is no cost for the plastic. If a recycler has to pay for the plastic to be recovered, this must be added to the total cost.

Cost reduction. The plastics industry needs to examine how to reduce costs. These costs are independent of the cost of the raw material going into making plastics. Already local recyclers who use the plastic in the same plant that recycles the waste tell us they can save the recycler profit, pelletizing and delivery costs. Their total costs are in the 17 to 25-cents- per-pound range. Also some recyclers claim the waste they use comes to them already sorted by the consumer. saving another 2 to 3 cents per pound. These are special cases and will not be the norm once recycling becomes big business. For this to happen, the emphasis on putting in recycling facilities needs to shift from the raw material supplier to the fabricator. If we plot these costs versus the selling price of virgin material,

TABLE 1 --Economics of plastics recycling

Cost item Centsnb Raw material cost 0 Collection of plastic 5-6

Sorting by major plastic type 2-3 (i.e.. PET, HDPE. water, orange juice and milk bottles, HDPE detergent bottles, HDPE base cups and HDPE bleach bottles)

Grinding 4-6

Washing and drying 6-10

Recycler profa 3 - 6

Pelletizing 8 Delivery in HC, EORl 2

Recycler cost 17-25

Market price for resin flake 20-31

Market cost for nonrefortified pellets 30-41

Hopper cam. east of the Rockies

Hydrocarbon Processing, May 1990 89

7 1 7 1 I 1 I I I I I I I I I I I '83 '85 '87 '89 '91 '93 1995 '81

Year

Fig. 2-U.S. plastics sales.

we find there itre periods bvhere recycling \vould not have bcen very profitable.

Most buyers feel the recycled material should sell at it

discount of about 10 cents per pound below virgin material. These buyers believe there are real quality dilkrences. Lot- to-lot variations may be wider. The dirt count may be higher. The color ma); be slightly 011. There may be impurities in recycled products that are not found in virgin material. And the material does not meet FDA standards for food contact applications. As long as polymer prices stay in the 40-cent- per-pound range or higher, recycling projects seem viable. But \\.hat happens if prices return to the low 30-cents-per- pound range? M'ill someone have to subsidize recycling? Will cities do this since they will no longer have the burden of the cost of collection. transporting the waste to the landfill and saving the cost of operating the landfill? Or will the plastics industry have to find some method of solving this problem?

Petrochemical feedstocks. Plastics currently use about two-thirds of all the petrochemical feedstocks produced in the U.S. If 25 percent of plastics are recycled, this is equivalent to increasing the capacity to produce resins by close to 25 percent. But it is foolish to assume there will be a magical 25-percent increase in demand. Therefore, demand for virgin raw materials will decrease by the amount of recycled material returned to the marketplace. At this time, we feel a goal of 25-percent reduction in solid waste will take a lot longer to accomplish than the politicians in Washington would like. Hopefully, 25 percent of the packaging market by 1995 is realistic. Packaging represents only 31 percent of the total market for plastics. If this goal is achieved, this would account for a total plastics recycling rate ofjust under eight percent.

Fig. 2 shows the total plastic sales in the U.S. from 1979 to 1989'and forecasts from 1989 to 1990 at four percent per year. At this growth rate in 1995, total sales will be 33.4 million tons. Eight percent of these sales is 2.7 million tons, which will then be recycled. In this scenario, the growth rate for production of virgin plastics will then decline to 2.56 percent per year. The major polymers that will be recycled will be PET, HDPE, polystyrene, LDPE and PVC. The growth in demand for these products will drop 1.5 percent to 2.0 percent AAI because of recycling material displacing virgin material.

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The speaker William C. Kuhlke is vice president of polymers for DeWm & Co., Inc., Houston, Texas. He pined Dewinin 1986after33years wrthShellOllandShel1 Chemical. In 7984, he was elected presdent of the Society of Plasttcs Engineers and is a distinguished member d SPE. Mr. Kuhlke has also served as vice president of olefins for DeWitt.

If indeed this scenario unfolds, are all the resin and feedstock plant expansions currently under construction needed? Banning. To force this scenario to unfold, politicians have a strong weapon-banning. The politicians are considering bans on various packaging applications involving polystyrene, polyethylene and PVC. But what are the alternatives if plastics are banned? In most cases, the volume of the competing material is greater and the competing material is more costly than that of the plastic. Since products do not degrade in a reasonable time in landfills, as people are led to believe, adding degradable additives does not appear practical. Of course, before much effort is expended on degradability, a standardized test procedure is needed to measure this prop- erty. ASTM currently has a committee assigned to this task. Until degradability is defined and measurable limits established, the marketing of plastics under a "degradable" label could eventually give the industry a black eye. Be cautious.

The third alternative is incineration with possible use of the heat generated to make power in the form of steam or electricity. It has been estimated that if all plastics are incinerated, enough electrical energy could be produced to light every home and office in the United States. A pound of polyethylene contains 43,600 Btu. A pound of coal contains 25,400 Btu. The waste disposal industry also claims that if incinerators are operated at proper temperatures and have modern gas treating systems, air pollution can be controlled to reasonable levels.

As for incinerator-bottom ash, industry is finding substitutes for lead and cadmium and the use of these products in the manufacture of plastics will decrease in the 1990s. It is too early to forecast the demise of these products, but the plastics industry has proven to be very resourceful in solving problems once they are uncovered. Members of the plastics industry live here too and also want a clean environment. A real Issue. In summary, the waste disposal issue is real and all plastics are involved. The plastics industries are working to reduce the amount of material going into the waste stream. Note that both source reduction and recycling involve the use of less hydrocarbons. The burning of trash in an incinerator equipped to use the heat generated to make electricity backs out the use of other fuels so all the solutions involved lower the use of hydrocarbons. Another way of putting it is that the removal of plastics from the waste stream plus the burning of plastics in incinerators promotes conservation of nonrenewable energy resources. The plastics industry cannot, however, do it alone. I t needs to work with the waste disposal industry to assist in the collection process and with the political community to possibly subsidize recycling. Where recycling is not feasible, proper, and I underscore the word proper, incinerators need to be built. Proper incinerators are operating in Japan and Western Europe. Why not America?

To solve the waste disposal problem in the U.S., three actions need to be accomplished by the plastics industry. Number one: Source reduction needs to be emphasized and implemented, and the result publicized to the political community and the consumer. I see very little evidence of this happening. Number two: Recycling programs need to move ahead faster. Number three: The waste disposal industry needs to be encouraged by the plastics industry and i t needs to build new incinerators. m

ACKNOWLEDGMENT Adapted froin a paper presented at the I990 Pelmchmrral Rnwi

rontcrcncc, D c h ' t t t & Co , Inc , Houston. Tcuab. hlarcti 27-2'' IO00

c

‘ SPECIAL REPORT

CMA members attack waste Wasteminimization. Resource recovery. Recycling. These are the uatchwords member companies are using as they tell CMA what they are doing to protect the enuironment. Some of the programs have been in place for years. Others are recent ventures to implement Respom*’- ble Care’sq” Pollution Prevention Code or to comply with prouisions of SARA Title I I I . Together, the actions and attitudes described here form a powerful mosaic that shows the environmentalists at work in the chemical industry.

Walter R. Quanstrom, vice president for environmental affairs and safety for Amoco Corp., believes that one of the biggest factors in Amoco’s environmental leadership is a major commitment to pollution prevention and waste minimization.

Writing in a recent issue of the com- sanfs Span magazine, he notes that imoco Chemical Company’s

Chocolate Bayou plant near Alvin, Tex., cut waste generated per pound of product 55 percent between 1987 and 1989.

A large part of the reduction came by substituting a polymer for lime in the plant’s wastewater treatment, dimin- ishing the generation of sludge.

Amoco Chemical also has found markets for secondary materials that once would have been discarded. The company now seIls a polypropylene waste, spent aluminum chloride, polypropylene xrap, spent caustic, waste terephthalic acid and wastepaper.

Quanstrom points out that Amoco Chemical recently announced a goal of eliminating hazardous waste from all of its more than 60 facilities worldwide.

Pollution prevention takes many forms at Ashland Chemical Company.

m Two of its subsidiaries together reclaim about eleven million pounds of plastic waste each year. They buy the scrap from suppliers and turn it into useful produck

m A number of products have been reformulated to ensure safety and environmental acceptability. For instance, a cleaning agent for diesel engine cooling systems was reformulated to remove a suspected carcinogen.

m An Ashland plant in Canada has installed an incinerator that eliminates odors and waste. Heat from the operation provides the plant with a new steam generation system.

In Calved City, Ky., ATOCHEM North America is building a new

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Air strippers at ATOCHEM Sortit Amrncai plont in Clowrt City, Ky.. will c7it inethyl chlorojorni i n uavtcwatcr.

wastewater treatment unit that will remove minute amounts of meth!d chloroform and other organics from effluent streams.

Using air stripping technology, the new unit will help ATOCHEM comply with its discharge limit for methyl chloroform of three parts per billion.

ATOCHEM also has started D ~ U C - $ ing hydrochlorofluorocarbon iHCFC 5 141b) as an alternative to chlorofluoro-

carbons (CFCs). ’ E The company says its substitute has

about one-tenth the ozone-depleting

CIBA-GEICY Corp.’~ plant in St. Gabriel, La., has earmarked $50 million for environmental protection, - including $30 million for a new solid waste incinerator.

The spending program will reduce waste currently generated at the plant - 50 percent and scale back landfilled wa.te 80 percent.

In one recent year, St. Gabriel reduced solid waste 25 percent. Further reduc-

8 potential of some CFCs. d

.\larch 1!11)1 CMA NEWS 3

I . SPECIALREPORT

calcium carbonate and calcium sulfate to counterbalance acidity in their soil.

St. Gabriel also cut emissions of tolu-its major Title I11 compound- by 29 percent on a per unit production basis. The plant has discontinued the use of methylene chloride, eliminating a waste stream that totaled 25,OOO pounds annually.

Overall, St. Gabriel has used process changes and improved engineering controls to achieve a 35 percent cut in its total Title I11 air emissions per unit of production.

Dow Chemical U.S.A. started a Waste Reduction Always Pays (WRAP) program in 1986 to formalize its ongoing waste reduction activities. Dow encourages employees to participate and honors several projects each year with Outstanding Achievement Awards.

One of the most recent winners is the

Rohm and Haas The World Environment Center has chosen Rohm and Haas Company to receive its 1991 gold medal for international corporate environmental achievement.

Presented annually, the award recog- nizes a company’s ongoing commitment to enhance and protect theenvironment.

The World Environment Center (WEC) is a nonprofit organization that encourages government and industry to work together to improve the environment.

WECs award jury cited Rohm and

Louisiana Division in Plaquemine. The plant installed a barge vent recovery system that captures hydrocarbon vapors released when products are loaded into low pressure barges. The vapors are returned to the original production process for reuse.

This project prevents more than lOO,(lOO pounds of hydrocarbon vapors from entering the atmosphereeach year and lowers potent ia l personnel exposure.

WRAP and other gnvironmental efforts have helped Dow reduce air emissions from its U.S. plants more than 50 percent since 1984. And the cam- pany is committed to reducing its 1988 SARA air emissions 50 percent by 1995.

Getting employees involved in the WRAP program embodies the personal philosophy of Frank Popoff, Dow’s chairman and CEO. He says: “I don’t

wins gold medal Haas’s environmental policy, established in 1966, as “visionary.” The jury also noted the company’s efforts to prevent pollution by designing production processes that generate less waste.

Lynn Johnson, corporate environmental director, said the award is “a strong indication that we’re on the right track.”

Several CMA members are among six previous winners of the award. They include Dow Chemical Company, the Du Pont Company, Exxon Corp. and 31.1. C W

want to be known as this company’s chief environmentalist. I want to be known as one of 62,000 Dow emsiron- mentalists. ”

The Du Pont Company has long practiced waste minimization, believing it is both environmentally responsible and good business sense to consene materials.

For instance, Du Pont recovers nearly one billion pounds of polymers each year through its manufacturing processes.

Waste minimization is the first priority in Du Pont’s hierarchy of respon- $ble waste management. The objective is to eliminate waste before it is made.

Du Pont manufacturing facilities have reached an earlier goal of reduc-

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4 CMA NEWS March 1991

A ~ 0 t h aditbvtv a trial miclmwe around spintiing ritachina at Tmncs~c Eatman Companyi phnt in K i n w r t . The enclawres hoof already reducedfirgitiw erniscionr of met on^. I ing hazardous waste a t the source 35 percent between 1982 and 1990.

Then in 1989, Du Pont board chairman Ed Woolard issued a new challenge to reduce all wastes 50 percent by 1995 and 70 percent by 2000, using 1982 as the base year.

All company sites that generate hazardous waste are required to develop waste minimization plans and to report progress annually. Du Pont provides help through a corporate program of education, training, data base resources and technology support.

A $2 million pilot project is currently underway a t Tennessee Eastman Company’s plant in Kingsport, Tenn., that the company believes will significantly reduce acetone emissions by 1993-two years ahead of its schedule.

Eastman’s initial goal called for a SO percent reduction by 1995. Although

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it’s too early to estimate the exact reduction, a company team that has been studying control technologies expects “a major reduction” from this project.

This phase, slated for completion by mid-1991, will fund engineering and construction for additional prototype systems that will enclose machines used to process acetone. Fugitive emissions captured by the enclosures will be recycled.

If the pilot project works as expected, actual improvements will begin later this year at a cost of $20-$30 million.

Acetone is a widely used industrial solvent. Eastman uses it to dissolve cellulose acetate to dope for filter tow and filament acetate yam. Thecompany already recovers and recycles almost 97 percent of the one billion pounds of acetone i t iises each year.

Ea5tman has also made significant

reductions in emissions of other chemicals covered by SARA. They include ethylene glycol, butyraldehyde, toluene. acetaldehyde and methyl isobutyl ketone.

At a recent stockholders meeting, Ethyl Corp. vice president for health and environment Gary L. Ter Haar said, “Ethyl’s strong environmental program costs a lot of money-an investment well worth making.”

Ethyl’s capital investment in pollution controls before 1986 was nearl!. $90 million. The company spent another $40 million through 1990.

“We plan to spend an average of about $25 million in each of the next three years,” Ter Haar said, adding that annual operating costs forenviron- mental controls represent another $2.5 million.

According to Ter Haar, “Theseefforts

1 March 19!ll CMA NEWS 5

T SPECIAL REPORT

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This unit ut CAF C h i c p k COT. ruydes annually 10.2 million pmrnds ofjonncr w d c .

have significantly reduced emissions to the air, concentrations of material into wastewater and disposal of hazardous waste.” He pointed to severd success stories.

“From 1980 t o 1989, our Orangeburg, S.C., facility had a 50 percent reduction of volatile organic materials despite a significant increase in manufacturing capacity.

“Ethyl’s Hardwicke Chemical operation in Elgin, S. C., in a joint project with our Magnolia, Ark., plant, has recovered nearly one million pounds of bromine, which had been discharged to the wastewater ?stem each year. I “In a program began in 1982, 1r.e

initiated actions to remove organic materials from the ground of the

former Baton Rouge (La.) tetraethyl lead plant site. TO date, we have removed about three million pounds, thus preventing them from moving off the plant site.”

Speculating on the future, Ter Haar believes “Only those companies that are aggressively committed to protec- ting health, safety and the environment will survive.

“In the years to come,” he told the stockholders, “I see a more rational view of environmental issues. I see more cooperation between industry and the environmentalists, with an ultimate goal of working on issues that matter most.”

T h e GAF Chemicals Corp. in Calvert City, Ky., has started a recycling unit that will distill and purify 10.2 million pounds of ethanol and acetone each year for reuse within the plant.

In the past, GAF had sent waste ethanol and acetone to a cement kiln where it was used as fuel. While this practice was environmentally sound, GAJ? recognized that the cost of new material, added to the increased cost of transportation and disposal, made mycling cost effective.

The recycling unit uses a basic distil- ling process that heats the waste, turning it into a vapor. The material is then cooled, filtered and returned to its original form.

“This is recycling at its bat ,” said CAF waste minimization engineer Jamie Leonard.

Waste minimization and recycling are uppermost on the minds of the 1,700 employees at the CE Plastics plant in Mount Vernon, Ind. They have aggressively adopted both programs in the past few months and, more importantly, are changing the way they think.

“You can’t even throw away a piece of paper or an aluminum can without thinking about the environment,” com-

mented one technician at the plant. Each employee work area has a

receptacle for recyclable paper, and each conference room contains a box for soft drink cans. These are collected and recycled by a local work center for disabled adults.

The company recycles more than 30,OOO pounds of cardboard and office paper every week, materials that formerly went to a landfill. Even wooden pallets are sent out for repair and recycled.

The keys to effective recycling, the company said, are to keep the programs simple and to segregate waste at the point of origination..

“These programs are not intense money-making ventures,” said Bert Contractor, manager of resource optimization programs. “Their real value

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6 CMA NEWS h4nrch 1991

lies in creating an understanding that one person can make a difference. Our experience has been that one contribu- tion to waste minimization leads to ideas for many more.

“For example, in the past nine months, we’ve seen a 54 percent reduction in the amount of hazardous waste sent for off-site disposal. This is a direct result of increased awareness.”

GE gave all employees the most recent facts and figures about waste disposal and SARA reportable emissions and empowered them to improve them.

Employees brainstormed ways to reduce pollutants in their operations. Some ideas were implemented immedi- ately. Others were collected for further study.

Said Contractor: “The spirit and enthusiasm for recycling and resource optimization has been overwhelming.”

Grace Specialty Chemicals Company has announced plans to reduce its missions 50 percent over the next five fars as part of its ongoing commit-

ment to waste minimization. This follows an emissions reduction

of nearly the same amount47peroent- that the company achieved in 1988, the latest figures available.

Grace president Donald H. Kohnken said, “We have an ongoing program to substitute materials in the manufacturing process that reduce the generation of hazardous waste, as well as modifying certain processes.”

Other pollution prevention actions Kohnken cited include treating waste to make it less harmful, reusing material where possible and reviewing new products in their developmental stage to reduce waste before production

Grace has doubled the number of people working on environmental initiatives over the past five years and invested more than $80 million in these

-orb last year alone. is an example of )mmitmd ace plans to instal rmaI a stion system at its G- Chemicdars

division plant in Owensboro, Ky., to reduce butadiene emissions more than On wcent.

e latex polym tion facil- eniissions met and state

begins.

Huntsman Chemical COT. racydcJ many materials, induding used glass and scrap poiystyene.

regulations, but the company says it is going beyond compliance to better protect the environment.

The new system, expected to be in operation by the middle of this year, will convert butadiene into harmless carbon dioxide and water. Division president Edward G. Najjar said the company is studying the feasibility of using this system to reduce other plant emissions.

The plant recently installed another

device to capture and emissions.

Hercules, inc.’s and CEO David S. believes that corporations more than required

“We must set a ourselves and live by it and talk about it,” he said during ceremonies honoring the Hercules plant in Hattiesburg, Miss., for environmental achievements.

Huntsman’s efforts win award Huntsman Chemical Corp. is a first place winner in Virginia’s Take Pride in Americaprogram. The award honors groups that have contributed to the increased wise use of America’s resources.

Huntsman was chosen for the 1990 award for:

w establishing and funding an environmental research center;

helping to develop the “Partner- ship in the Parks” program that established recycling in three national parks;

“adopting” and regularly cleaning a one-mile section of Virginia Beach near the company’s Chesapeake, Va., facility;

taking part in “Clean-the-Bay” Day to beautify Chesapeake Bay; and

educating the community about :cling.

In addition to helping clean the beach and the bay, the Chesapeake employees regularly clean the shores of the eastern branch of the Elizabeth River where the plant is located, removing old tires, bottles and other debris.

Huntsman joined the National Park Service for the Partnership in the Parks program to collect and recycle plastic, glass and aluminum containers from the Great Smokies, Grand Canyon and Acapj’a National Parks. The program als vides exhibitions, publications ant programs to promote recycling.

e possible, the recycled plastic will r,C. returned to the park in the form of such products as picnic tables, benches, sign posts, guard rails and car stops. The!. \vi11 look like \vood but are more d 11 raldc . enc

I I . SPECIAL REPORT /-

During 1989, the plant reduced effluent solid discharges 99 percent, effluent biological oxygen discharges 97 percent and wastewater flow 50 percent. It also eliminated 140 tons of sulfur dioxide discharges and 700 tons of particulate emissions annually.

Hercules has developed several major businesses based on using waste materials. Rosin and fatty acids are recovered from crude tall oil, dulose derivatives from wastecotton lint, pectin from citrus peel and naval stores from pine stumps.

Hoffmann-La Roche Inc. says it is more than two-thirds of the way toward its goal of cutting toxic air pollution at its factoris by 90 percent.

Fugitive emissions from unidentified valves and flanges account for most of the problem. The wmpany has cut fugitive emissions at its Nutley, N.J., plant by an average of 64 percmt.

Methylene chloride emissions were reduced more than 90 percent and toluene emissions by 70 percent between 1987 and 1989 at Nutley. During the same period, the Belvidere, N.J., plant reduced chloroform emissions 4 1 percent, acetone 82 percent and toIuene 52 percent.

Hunkman Chemical Corp.’s recycling program a t its Chesapeake, Va., manufacturing facility saved the company $1.2 million last year and kept more than 11.5 million pounds of material out of local landfills, a 60 percent improvement over 1989.

The recycling program, part of

Ecology group lauds Monsanto Monsanto Company recently received the h a k Walton League Award for its program to reduce toxic air emissions 90 percent by the end of 1992.

“Monsanto Company was unani- mously seIected by our awards committee for its efforts to reduce emissions well beyond what the (old) Clean Air Act would require,” said Jack Lorenz, executive director of the Izzak Walton League, a national environmental organization. C W

Huntsman’s waste reduction plan, covers a broad range of materials. It includes scrap polystyrene from the manufacturing process, machine lubricants, cleaning solvents, metal and fiber drums, wooden shipping pallets, cardboard shipping containers, scrap metal, aluminum cans, glass containers and computer paper.

Employees also bring their used motor oil from home for recycling.

Plant manager James Joyce described the operation as “a win-win situ- ation. We save money and help pre-

serve the environment. And this is just the beginning. We’re getting better a1 it every year.

“We’ve had calls from other companies asking how we set up the program. We even gave a presentation tc the U.S. Navy,” he said.

The New York Tim& carried a long feature story in its February 3, 1991. edition, lauding the Minnesota Mining and Manufacturing Company (3M) for its progressive Pollution Prevention Pays program. The Times wrote: “Environmentalists and financial

analysts alike say that 3M, perhaps more than any other major American company, is dedicated to cleaning up after itself through a program that provides case study examples of how managers at all levels should handle environmental issues.

“It is nowhere near finishing the job, and continues to emit large quantities of toxic chemicals. But it has ambitious goals and a record of achievement. ‘‘ ‘They are one of the few companies

that have been doing the right thing for years,’ said Barry Commoner. director of the Center for the Biolog? of Natural Systems at Queens College and a longtime environmental activist. ‘They understand that the way to prevent pollution is to eliminate thc production of toxic materials.’

R CMA NFWX \4nrch 1991

made abundantly clear by several events including the catastrophic accident in Bhopal, India, and, in its after- math, the findings of Superfund‘s Toxics Release In- ventory.

The inventory requires industry to estimate and publicly announce toxic emissions, chemical by chemical and plant by plant. Industry had never before been required to report releases in this fashion.

And when the first inventory, for 1987, was released, corporate management was shocked by the billions of pounds of toxic pollutants-and dollars-that were going up the stack and out the pipe. Clearly, a reassess- ment was in order.

The prescriptive commandsontrol approach to controlling pollution has been successful to a point. It has eased egregious pollution while allowing for economic vitality, but it has a major drawback of shifting pollution from air to land to water and back again. It ’’bought time, but not much more,“ declares James G. Speth, former head of the Council on Environmental Quality and current president of World Resources Insti- tute, a Washington, D.C.-based think tank.

Technology-based regulations have left unsolved some awesome, intractable problems: global climate change and a thinning stratospheric ozone layer. Al-one, the regulations cannot correct these difficult, high-risk problems. In some cases, they may be coun- terproductive, “serving only to inhibit innovation and to discourage regulated industries from going beyond minimum legal requirements,” says EPA Administrator William K. Reilly.

The agency, Reilly says, needs to reassess the programs it administers and the tools it uses to find “the most efficient and effective ways to reduce risk.” Above all, he says, the agency has to make pollution preven-

VentioMnIented and companies are en- cwaged to cut pollution through SWCB reduction and irrprocess recyding. And fk nally, it is not media9peclfic: All releases to air, water, and land are to be reduced.

Howewer, it is hoped the effort will stimulate companies to make earlier reductions in their emissions of highly toxic chemicals-befae StaMay deadlines call for such wts-and prod them to reduce wastes at the 8ov#) ratheir than through treatment or dtsposel.

“Pollution prevention can be the most cost-effective alternative to atter-the-act treatment of pollution,” Reilly contends. “Companies can save on waste manags ment, reduce the use of raw materials, and minimize liability. And “ o v e r , by taking this approach, oompanies can help relieve themselves of regulatory bvdens.”

Companies can also gamer positive

tion the watchword for all its programs, “from mur‘ pal wastewater treatment to toxic air pollution to str ger, carefully targeted multimedia enforcement str gies to integrated, ecosystemwide programs such as , new initiative to clean up the Great Lakes.”

By prevention Reilly means a hierarchy of reduct and management practices. These focus on source duction first, environmentally sound recycling nl treatment if necessary, and disposal as the last resc- He expects prevention to play a major role in attain the safe, sustainable environment he seeks.

According to EPA guidelines, source reduction (

be accomplished through material substitution, prod - reformulation, process modification, and improv housekeeping. But EPA also includes what it calls en ronmentally sound, closed-loop recycling.

But changes other than pollution prevention w have to occur to reach Reilly’s ultimate goal of a SI tainable environment: new management and manuf; turing practices, conservation of resources, greater re ance on renewable energy sources, substitute materia and more durable consumer goods. Speth would add this list population stability, a rethinking of industr productivity so that prices reflect full environmenc costs, and “a fair sharing of economic and environme tal benefits both within and among countries,“ that social equity. 1

Speth expressed his views last month at the Coll quium on Industrial Ecology, hosted by the Nation Academy of Sciences and funded by the AT&T Found tion. Industrial ecology means “a systems view of il dustrial products and processes that considers the tot materials and energy cycle . . . in a way to minimize a( verse environmental effects,” explains AT&T Bell La1 executive director Kumar Patel. Colloquium organizt

publicity from their efforts. not an incentive to sniff at, says Wllliam M. Bwch, dep uty chief of the special projects office with EPA’S office of Toxic substances, which is managing this pollution prevention effort.

All In all this program appears to be a pretty enticing cat~ot. So far, about 200 companies have nibbled. including some of the giants of the chemical industry. (EPA is expected to release mon-posi- bty this week-its first accounting of com

prevention program.) Chemical companies that have sub-

scribed to the 33-50 Program include Amoco Chemical, BASF, Bayer, Dow chemical, Du Pont, Monsanto. occidental Chemical, and Union Carbide. Many, including W i d e . Du Pont, and Dow, have committed to even greater reductions.

pan& that have signed up for the pollution

Dow president and chief executive o ficer Frank Popoff says the company ‘’ looking foward to working with EPA on th landmark emissions reductknr campaigr We have found that voiwrtary reductio programs . . . are the best way to continu ously improve environmental p ” a n c t and achieve the desired results mor{ quickly than the traditional regulatory prc cess.“

Since 1986 Dow has voluntarily re duced emissions through its Waste Reduc tion Always P W (WRAP) program. T h i ~ companywide effort stresses source re duction and recycling and rewards employ 88s for successful programs. “DOW prob ably has the most aggressive pollution prevention program in the country,” say$ Joanna D. underwood, president of t k New York Cityaased environmental re. search group INFORM.

0 July 8, 1991 C(LEN

Lynn W. Jelinski, head of Bell Labs' biophysics research department, puts it more pithily: "It is a watershed in the way chemical engineers think about the environmen t."

Both Reilly and Speth are calling for nothing short of a complete dismantling of the throwaway society. A paradigm shift so basic that it calls for total rethinking and retooling of every societal activity. It calls for "continuing development and adoption of ever less polluting and more resource-efficient products, processes, and services," says Robert Repetto, an author of a World Resources Institute report, 'Transforming Tech- nology.'' And it requires exquisite planning and much patience over the long haul.

A good starting point, one taken by Reilly, is pollution prevention with a focus on industrial processes. But even to succeed in this narrow arena Reilly will need the support of the White House and Congress. And such support is not totally forthcoming.

Though the President's fiscal 1992 budget insists on his "commitment to effective pollution control," it doesn't discuss prevention. The President's budget also i does not address the funding of prevention efforts in

its discussion of the Great Lakes program. And even though Congress passed the Pollution Pre- ntion Act of 1990 in the waning days of the lOlst

ongress, "the ethos of pollution prevention has not ached Congressional ears," says Ann M. Mason, asso-

ciate director for the Chemical Manufacturers Associa- tion's environment division. Both she and William M. Burch of EPA's Office of Toxic Substances say Congress is taking a wait-and-see attitude. It is still uncertain whether industry can move more rapidly in a voluntary fashion than it does when EPA p.rescribes it to in a command-control approach. Still, Burch notes that

"there will be strong pollution prevention emphasis in considering renewal of the Clean Water Act and the Resource Conservation & Recovery Act [RCRA]."

The Toxics Release Inventory is credited with en- couraging prevention activities within industry, especially the chemical sector, the largest single source of toxic waste. Until the inventory, "companies knew what kind of regulated waste they were generating, but that's different from knowing emissions," which is information the inventory gave them, says John 8. Atcheson of EPA's Office of Pollution Prevention. Once companies were able to relate emissions to a process system, they were able to see opportunities for curbing waste, and thereby increasing operating efficiency, Atcheson remarks. As Michael R. Deland, chairman of the Council on

Environmental Quality, explains, companies practicing pollution prevention will reap untold benefits, not the least of which is a more competitive position in global markets. Domestically these forward-looking companies will be able to bask in the glow of warm publicity while foregoing the burdensome costs of regulations and litigations, he adds.

EPA made its own cultural shift in 1988 when it established the Office of Pollution Prevention, within the Office of Policy, Planning & Evaluation, to promote a p propriate multimedia strategies within EPA, other federal agencies, and industry. Within the next several months the prevention office is to merge with the Of- fice of Toxic Substances, a reasonable move since toxic chemicals are the focus of the prevention effort.

The prevention office performs a multitude of tasks, including the awarding of grants totaling about $7 million to states for appropriate prevention projects. Some states, with prodding by environmental groups like the

Carbide's chairman and chief executhre officer. Robert 0. Kennedy, believes, "The chemical Industry Is playing a major role in helping Mr. Reilly achleve hls vlslon for greater reduction of polhnants ttwough voc untary industry actlonr." In turn, Reilly Says the chemical Manufactuers Associ- ation's Responsible Care pro~em is help lng indurtry play this central rde. Indeed. when announcing the 33-50 poiiuUon we- vention program, Reilly clted Responsible Can, as a signitkmt voluntary effort ai- reedy under way.

Despite its general suppat for the 33- 50 Program, industry still has some anxiety about how voluntary reductions will relate to state policb and other federal pro- gams. especially the C l m Air Act, notes bra

Expanding on thk, Ann M. Mason, associate director of CMA's environment divi-

sion, explalns that companies want to better understand whether their ability to comply with the Clean Air Act, the Clean Water Act, and other laws wlll be impatred by a voluntary commhnt to pollution prew#ltion. They are also unclear how the new climate of voluntary reductions will work va-v is the old culture of c0"anCc andumtrol. "There are bound to be a few incompatibilities while we are between the two cultues," she says.

EnvkoMnentai grwpshave other concems. The ones related to John Atcheson. chief of the prevention integation branch of EPA's Office of Pollution Revention, fall into three areas. Some wlthin the environmental community have fretted about the issue of voluntary versus mandatory reduc- tkms. have expressed concern that reductions of 33% and 50% may be too limiting, and have wondered whether reduc-

tions of ail chemicals listed on the Toxics Release Inventory wouldn't be better than limiting the cuts to a mere 17.

As Deeohn Fecris. director of the Na- tional Wildlife Federation's envkonmental quality division. explains. "Pollution pie- ventkn Is a commendable approach. But whet we are concerned about Is account- ability. Volu"rcery me~sues are fine but we would like some accocnting of the measures taken by industry to reduce pollution." Lois N. Epstein, an environmental engineer whh the Environmental Defense Fund, adds, "The voluntary approach is a good first step but we also are working with other members of the environmental c0mmunQ to get a slightly more mandate ry toxic u98 reduction program In place."

under a Ferrkipsteln approach, com panies would be able to set their own goals for meeting a govemmentmandeted

July 8. 1991 MEN 9

- _ News Focus

-_-- EPA, Amoco join forces to ferret out ways to cut refinery wastes

An environmentally sensitive locale- hard by the Chesapeake Bay, directly across the York River from the Virginia Institute for Marine Science-is indeed an incongruous setting for Amoco's Yorktown facility. Yet daily for 35 years-some 13,000 days--the facility has refined about 53,000 barrels of crude oil with no major mishap. Its prin- cipal products are gasoline, heating oil, petroleum coke, liquefied petroleum gas (Lffi>--and an unlntended I million Ib or more per year of toxic chemicals released into the environment, mainly into the air.

In 1989, the Environmental Protection Agency joined forces with A m "to try to look for opportunities for holistic environmental management using real data at a real facility," explalns Deborah M. Sparks, program development coordinator In Amoco's environmental affairs and safety department. The slightly more than $2 mlllion study will emphasize pol-

lution prevention opportunities and may accrue a bonus for the refinery-Amoco may be better able to order its capital planning for environmental investments.

Before pollution can be prevented, it must be identified. So the first phase of Amoco's project. begun and completed in 1990, involved gathering information on refinery emissions and their sources. Linking emissions to sources allows for prevention solutions: processing changes to reduce emissions or source elimination to minimize pollution releases.

More than 1000 environmental sam ples have been collected and subjected to up to 20 separate analyses. The results are now being evaluated and will be peer reviewed by consultants brought together by Resources for the Future (RFF), a Washington, D.C.-based think tank. RFF was hired by EPA to conduct independent assessments of the project.

The second phase, developing. model- ing, and analyzing engineering options

such as changes to processes, cont equipment, and operating and main1 nance practices. is now under way a should be completed by the fall. The options, some of which may actually I

installed at the refinery, are being ar b e d for cost, technical and regulatc ~

(permitting) feasibility, and safety. Partl ipants hope to better define existing ai- potential incentives and barriers to ex cuting these options.

RFF consultants are also expected review these possible technical sol tions. But even before this review, Am co is already considering implementing number of the options, says the firm project director, Howard Klee Jr. The rc finery is looking at changing the c d t i r process to reduce the need for the watt pond, thereby reducing air emissions I

volatile organic chemicals. It is addir additional seals to its storage tanks 1 reduce vapor losses. And it hopes to in prove the oil/water separation' systei

. ~~

Public Interest Research Groups (PIRGs), have very strong pollution prevention programs. Others are seek- ing funds for research or demonstration projects, which EPAs grants may underwrite.

State programs that local PIRGs lobbied for are stron-

gest in Massachusetts and Oregon, which passed toxic use reduction laws. In fact, some major national env ronmental groups have been urging Congress to p a similar legislation at the federal level. In California, th local PIRG helped pass the Toxics Use Reduction Inst.

tlmetable, but would have to repat on progress in meeting those goals. A simC lar program, which targets toxics use, is already in place in Massadwrsatts, explains Epsteln.

Therelsoneconcemshardbyboth emriroMwMtelgror48andcaporations: the switching of one toxk chemical for anather without etnvhnental gain. EPA Is expected to carefully scrutinize the 33-50 Program to make certain that doesn't happen.

what EPA hes not done to date 1s clearly spell out the relationship between reductions made under the vol~ntary 33- 50 Program and those required under the 1990 Clean Air Act amendments. Just last month, Reilly announced the 80- called early-reductions rule. As proposed, that rule would gtve companies six extra years to install stringent control

techoloey If they reduce gaseous toxlc air emissions 90% or toxic air particle emissions 95% before EPA Issues control stendards for their Industries ( W N . June 10, page 5). Reductions of some 189 lmrentory-listed chemicals (inciudlng the 17 under the 33-50 Program) would be measured against 1987 emisslons. EPA is expected to propose standads for the chemical InduslJy this "her.

Some in Industry are worried that reduced emissions under the 3 M O Pre ram wOUM be used as a baseline for complying with standards under the Clean Air Act. Thus. by not volunteering for the 33-50 Rogram, companies could have more room to make reductions required under the clean air law. unless the voluntary cuts are credited toward the mandated reductions.

This apprehension about credits as

well as worries concerning permit requirements and other issues were raised by the Rubber Manufactwers Assoclation and the National Association of Manufac- turers, and were relayed to EPA in a let- ter from Rep. John 0. Dingell @.Mlch.), chairman of the H o w Energy 8 Com mer- Committee. EPA has not yet offi- cially answered Dingell.

However, In r e m to Industry representatives and reporters. agency staffers have pointed out that reductions under the 3350 Program would not necessarily apply under the Clean Air Act, but emissions cuts made to comply with the air law would automatically apply to the voluntary Program.

Despite the lingering questions, EPA's Atcheson believes, "On balance the benefits of the voluntary program outweigh some of the concems being raised."

-

-

10 July 8. 1991 W

Atnoco’s rorklown plant Is $He of $2 mlUlon polhrllon prevmthm study

and underground sewers to reduce releases from these.

Because the YorMown facility could not meet Resource Conservation 8 R e covery Act (RCRA) conditions for disposing of its oily sludges and solid wastes, it began recycling them back to the coker.

Here, lighter oil components are recovered and blended into useful products, while heavier components and so l i are burned in the coker as fuel.

Klee admits recycling “was prompted by the RCRA standard, but it is the e a - nomically more sensible thing to do.” As

a result of reprocessing, the Yorktown facility produces 3000 bbl per year of oil products that previously would have been disposed of on its land, and, in addition, saves about $1 million per year in disposal costs it would now have to pay to haul the wastes to a RCRA-approved landfill.

The project will end with a final report released at the end of the year. Klee hopes the study will provide “a much better picture of the kinds of issues we need to deai with in a refinery; in short, a good database to study and think about alternatives.” He would also like others to use the study’s resuits to assess their own facilities.

And finally, Klee would “like to see more government-industry cooperative efforts.” As it now stands, the €PA-Arm- co study is a unique venture, the first time the regulator and the regulated have combined forces to contribute money (75% Amoco, 25% EPA), personnel, and time to the same project work plan, he explains.

tute Act. This law requires the University of California to create a center to research alternatives or substitutes for toxic chemicals in industrial processes.

Jointly with the Department of Agriculture, EPA is awarding $2 million in grants for sustainable agriculture. Along with the Energy Department, EPA is funding grants to projects researching and demonstrating energy efficiency and waste reduction.

In an outreach education effort, the agency has developed the Pollution Prevention Information Clear- inghouse, accessible through personal computers. The prevention office also publishes and distributes a free monthly newsletter.

EPA also set up the American Institute for Pollution Prevention in 1989 under a cooperative agreement with the University of Cincinnati. The institute functions as a nonadversarial bridge between industry and EPA. Members, who volunteer their services, are experts representing about 50 trade associations and professional societies, including the American Chemical Society.

The institute‘s mission is to act as the lubricant that eases the spread and adoption of pollution prevention concepts within public and private sectors. Gerald Ko- tas, head of EPA’s Office of Pollution Prevention, calls it “the grounding strap to reality for the Administra- tion and the agency.”

To carry out its mission, the institute divides into four groups: the economic council, headed by Robert B. Pojasek who represents ACS and who was just voted new institute chairman; and the education, implementation, and technology councils. The former chairman

was Joseph T. Ling, retired vice president for environmental affairs at 3M, who is sometimes called the father of pollution prevention. Managing the daily operation of the institute is Thomas R. Hauser, formerly with EPA.

Groups with a similar goal, though not linked directly with EPA, have also been set up. The American In- stitute of Chemical Engineers launched the Center for Waste Reduction Technologies in 1989. Its aim is to help “industry in its efforts to meet the challenge of waste reduction” by developing clean technological systems, explains center director Lawrence L. Ross.

A more training-oriented center, the Waste Reduc- tion Institute for Training & Applications Research was founded in Minneapolis in 1990. Its primary focus is on instructing federal, state, and local regulators of waste, as well as those in industry who manage the generated waste. But it also conducts applied research on waste reduction options.

EPA‘s Office of Pollution Prevention began its myri- ad activities even before it and its mission were formal- ized in the 1990 Pollution Prevention Act. Rep. George E. Brown Jr. (D.-Calif.), chairman of the House Science, Space & Technology Committee, terms the new law “an important departure from the school of environmental remediation philosophy.” He sees it as a prod for “making environmentally benign choices for front-end materials . . . (for] transforming waste into salable new products.”

In addition to legitimizing the pollution prevention office, the new law also required €PA to develop and publish a pollution prevention strategy, which the

July 8. 1991 =EN 11

News Focus

agency did in February. The strategy sets forth EPA‘s future direc- tion in multimedia source reduction, emphasizing flexible, cost- effective approaches and market- based incentives.

The first part of the strategy is the 33-50 Program, so-called became its goal is to cut emissions of targeted chemicals 33% below 1988 levels by the end of 1992 and 50% below 1988 levels by the end of 1995. But EPA is in the process of developing prevention programs for agriculture, energy and transportation, the consumer sector, and the federal goven- ment.

For agriculture the focus will be on low-input sustainable projects, integrated pest management, and integrated crop methods. In energy and transportation, the focus will be on efficiency in lighting, machines, and motor vehicles. The federal government programs will target procurement specifications to prod the demand

CMA’s Responsible Care program targets wastes

In 1988, the time was ripe for the cbm- ical industry to reassess the need for environmental stewardship. The accidents in Bhopal, India; Institute, W.Va.; and other sites had heightened public apprehen- sions and focused Congress’ attention on the industry. AS a result, when Congress renewed Superfund in 1986 it added a provision requiring industry to report toxic emissions released into the environment.

The resulting Toxics Release Invento- ry opened corporate management’s eyes. By 1988 a database existed that tallied how much toxic waste was being emitted into the air, water, and land. Cor- porate America frankly seemed to be shocked by the quantity. Grass-roots efforts to eliminate these emissions to communities surrounding chemical facili- t i s took on greater force. Industry knew it had to take note and respond.

And respond the Chemical Manufac- turers Association did. with a program it calls Responsible Care: A Public Com- mitment. CMA’s 185 member companies must commit to a set of guiding principles that blanket every operation at every chemical plant.

These principles oblige members to improve their chemical processes, prao - tices, and procedures to reduce every possible waste, emission, or accident. and to communicate their efforts to the public. They also must be responsive to public scrutiny and concems. if they fail to carry out these principles. they lose their CMA membership.

To implement the principles. the Re- sponsible Care program codifies six management practices, one of which is pollution prevention. While giving preference to source reduction. CMA defines pollution prevention to include in-process

f& clean techndlogies. And for the consumer sector, the aim will be defining ways to assess health and environmental impacts over a product’s life cycle.

An important element of the Pollution Prevention Act is the requirement that companies begin immedi- ately to quantify their efforts to curb waste through source reduction, as well as through recycling and treatment. €PA expects the Toxics Release Inventory plus this new requirement to further persuade companies to undertake voluntary reduction actions.

One company that needs no convincing is 3M. In 1975 it ”started to see an increase in environmental costs. To those of us with engineering backgrounds, the alternatives were to continue to increase capital spending on pollution control or to get people to develop new products, new processes to eliminate pollution,” says Thomas Zosel, manager of 3Ms pollution prevention programs. The logical decision was to develop new ways to cut pollution, and thus was born 3M’s “Pollu- tion Prevention Pays” program.

Close to 3000 individual projects have been recognized under the Pollution Prevention Pays program since 1975. And according to Zosel, pollution releases and energy use have both been reduced 50% since 1975, at a savings conservatively estimated at about $530 million.

Despite these results, 3M has a long way to go. The company is still one of the highest emitters of toxic pollution, according to the Toxics Release Inventory. Recognizing the need for further reductions, the company has instituted a new program called Challenge 95. Zosel says the short-term goals call for a 7% per year reduction in emissions over the next five years.

Another company, Dow Chemical, has a long history

12 July 8. 1991 C6EN

of taking care of its considerable quantity of toxic waste. Control programs were put in place in the 1930s at its first plant in Midland, Mich. In the early seven- ties, at its own initiative, Dow mandated a corporate- wide policy of incinerating all organic waste instead of injecting it into deep wells, as was then industry practice.

A year after being asked by Rep. Henry A. Waxman (D.-Calif.), chairman of the House Subcommittee on Health & the Environment, for data on its total emissions-and then being startled by the results-Dow instituted its Waste Reduction Always Pays (WRAP) program in 1986. This program is geared to instill a waste reduction mentality in employees from top manage ment to process-line operators. Its goals are to reduce releases to the environment in a cost-effective manner to encourage creativity among all employees, and tc award (with Dow stock) employees for successful inno vative projects.

Results have been excellent, and noted by the Offict of Technology Assessment and environmental groups Dow in 1990 approved 115 WRAP projects at a cost o $13.2 million. First-year savings are pegged at $18 mil lion, or a return on investment of about 125%. Of thi- 115 projects, 53 were specifically pollution preventioi activities, with a return on investment calculated to b 109%.

EPA’s. According to John S. Kowalczyk, WRAP manag er at the Midland site, “first eliminate the waste, seconi recycle it, third treat it by incinerating it, and fourt dispose it” in approved, company-owned landfills. Th option of last resort is seldom used, Kowalczyk say “Dow built a landfill at Midland in the early eightie

Dow’s waste management hierarchy is similar tl-

and off-site recycling, and treatment. says Ann M. Meson, associate director of CMA’s environment division. The Envi- ronmental Protection Agency focuses on two primary strategies: sowce reduction and closed-loop recycling, Mason explains.

The other principles require that companies communicate with their employees and the public: coordinate emergency response plans with local officials; safely transport materials outside the “fence line” (plant perimeter); ensure worker health and safety; decrease accidental releases from process equipment inside the fence line; and ensure product stewardship beyond the fence line.

“A different climate is emerging with in our industry,” explains Mason. “As we work with and reflect on Responsible Care. we are recognizing areas for im pmvement. The program has been a cat-

alyst because its stated goal is improved performance, and the measurement of that is the response of the people living around our plants.”

“To be quite candid,” she adds, “We didn’t do things right in the past. Today the chemical industry is really trying to change and to adopt a different ethic.”

Joanna D. Underwood, president of the New York City-based environmental research group INFORM, sees the Re- sponsible Care program as “a very bold initiative for an industry that hasn’t been bold on such an issue. The biggest question is not the shape af CMA’s program but the response of companies.” But, she adds, “Will they deal with the spirit of the initiative?”

Underwood offers this warning: Those companies that don‘t undertake the prao tices Responsible Care calls for will be out of business down the road.

sions 74% from 1986 to 1991, explains Louis H. Kistner, president of the Chemical Industry Council of Maryland. Among the 11 are Atochem North America, FMC Corp., Rh6ne-Poulenc, W. R. Grace, ’and Vista Chemical.

Vista‘s director of environmental control, David L. Mahler, cites one example of a successful pollution prevention effort. Vista’s Baltimore site makes surfactants for household powder and liquid detergents and uses large volumes of benzene, toluene, and xylene. Beginning in 1978, Vista focused first on controlling benzene air emissions. And to date, simply “by enclosing open systems, tanks, process vents, we have been able to reduce benzene emissions by 99%. We plan to reduce the remaining 1% by an additional 75% by the end of 1992,” he says.

Mahler contends the Baltimore facility “hasn’t saved a lot of money.“ But he quickly adds it‘s difficult to calculate benefits and sav-

that was projected to last to the year 2010. Now projec- tions are 2040,“ he says. This landfill is open only one day a week.

Sometimes a group of companies comes together to find ways to reduce their toxic emissions. This has happened in the south Baltimore area. Here 11 companies have combined forces to reduce their total toxic emis-

ings such as less future litigation and liability, and fewer regulatory fines. As these industrial waste prevention programs show,

the most successful occur when “environmental stewardship belongs to everybody at the plant,” declares CMA‘s Mason. This was documented in a 1986 study by the New York City-based environmental research

group INFORM. “Cutting Chemical Wastes,” a seminal work that along with an OTA study on waste reduction in- spired the 1990 pollution prevention law, concluded, “Obstacles to pollution prevention were institutional, not legal, economic, regulatory, or technological,” says INFORM’S president Joanna D. Under- wood. As Underwood explains, for the most

part INFORM found that, “the responsibility for waste management was delegated to the environmental control depart- ments. These were skilled in engineering disposal techniques but had almost no responsibility over what went into the plant that generated the waste they were supposed to manage.”

But that was then. Now, Mason contends, “a different climate is emerging within OUT industry.” Employees are now being encouraged to look beyond their immediate jobs “for creative ways of us-

Bmen (above): evolutionary move to pmvention mode. Deland: companies.

reap untold benefits

ing existing tools” to reduce pollution. Mason calls this “empowering the work force,” something embedded in CMA’s Responsible Care program. A set of guide-

July 8. 1991 C&EN 13

_- - - News Focus

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Analytical chemistry moves from lab to process stream A quiet revolution is taking place as analytical chemistry moves out of sophisticated laboratories and into the process stream. The joumey is likely to improve the global competitive position of manufacturing plants because of lowered product costs, enhanced quality, and minimum waste of raw materials and energy. Increased process efficiency also means releases are better controlled at the source and can be decreased, if not eliminated-an environmental plus.

This new subdiscipline goes by the name process analytical chemistry (PAC), the brutish cousin of traditional chemical analysis. Rugged and depen& able PAC analyzers are operationally and physically part of the process, and are used to optimize or control it-quickly.

PAC evolved as a solution to problems, and in recent years has profited from startling developments in micro- electronics, photonics (especially fiber optics), and chemometrics. Chemomet- rics is a way of handling, organizing, and analyzing data produced by the analytical chemist but used by the process engineer. It employs sophisticated statistical methods to determine practical relation- ships between process parameters (temperature, pressure, impurities, feed rates) and product performance.

"Most chemists think of PAC as buck- et chemistry, but an awful lot of changes have occurred." explains Joseph J. Breen. a chemist with the Environmental Protection Agency's Office of Toxic Sub- stances, and a co-organizer of an April American Chemical Society symposium on pollution prevention and PAC. For example, such sophisticated tools as FTIR, x-ray fluorescence, and plasma spec- trometers are being used in the process environment.

As progress occws. industries beyond the traditional users-the commodity chemical and petrochemical industries- ire beginning to see the value of PAC to

Mltchll (seated) and Y a m work on Iab-scak Ondunand arslne generation praces at AT&T research center

their bottom line. Many of the most fun- damental advances are being made at the unique Center for Process Analytical Chemistry at the University of Washing ton. Seattle.

Launched in 1984 with core funding from the National Science Foundation and 21 corporate sponsors, the center has turned into one of NSF's more successful stories: a clear channel for communications between university and corporate America. Indeed, there are now about 45 corporate sponsors, which, with NSF and the university, fund the center. In its short lifespan, the center has filed at least 14 patent disclosures for technologies ranging from refractive index detectors to multivariate infrared analysis to automated sample handling. 1 The aims of the center are twofold: to hook new measurement tools to state-of- thsart microcomputer technology and data processing capability to achieve real-time feedback control of process streams; and to train a new breed of students, process analytical chemists,

and engineers. To achieve these the c~nter must be multidisciplinary, ing on the tools of analytical cheq physical chemistry, chemical and ei cal engineering, mathematics and s tics. and computer science, and dra on the skills of facutty and corporate entists and engineers.

This "systems" approach, cente rectors Bruce R. Kowalski. Jame Callis. and Deborah lllman say, will to advaiices that enhance the c o r tiveness of the chemical and matc industry, and "make a significant c( bution toward proactive environml protection."

EPA's Breen wants to make sure message is heard. Along with Mick Dellarco of EPA's Office of Resear Development, he organized the symposium "as a tutorial to get chef thinking about pollution prevention new environmental ethic." For three ahalf days, symposium attendees t some 44 papers on topics ranging sophisticated new sensors and rob

lines and management practice codes, Responsible Care requires all CMA members to enhance worker and public health and safety by reducing al l toxic emissions through practices and process changes, and to communicate these efforts to the public.

Although a top-down philosophy of pollution prevention is beginning to permeate the chemical plant,

14 July 8, 1991 C6EN

other barriers still remain. Not the least of these i. Pollution Prevention Act itself. Writing in the lourn the Air 6 Waste Management Association, Aluminum of America's environmental programs manager R. Byers says the law addresses source reduction and e ronmentally sound recycling, but "leaves unaddre . . . where waste minimization resulting from reuse

_ -

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i--* Arsine (AsH3)

Drying columns I 1 t f

Powr supply control unit

On-line process control monitor

I I Product stream

# j )Mass flow controller

to industry success stories concerning applying PAC to real-world pollution problems. These papers are to be published next spring as part of the ACS Symposium Series.

AT&T analytical chemist James W. Mitchell. speaking to a Colloquium on In- dustrial Ecology sponsored by the Na- tional Academy of Sciences in June, e m phasired the need for industry to explore pollution prevention strategies in chemical processing and manufacture. Ever more stringent compliance requirements and escalating costs for waste treatment and disposal compel such exploration.

Mitchell says altematives to existing environmentally harsh technologies will focus on two possibilities: substituting more environmentally benign chemicals for toxic ones, or, when this is not possible, developing ondemand processes that make the toxic chemical only in the quantity needed for immediate use.

As an example of substitution, Mitchell cites methyl chloride, a high-volume commodity chemical that is being

phased out by the industry because of health concerns, among other reasons. Its replacement is likely to be "ethyl- 2-pyrrolidone. which has all the favorable properties of methyl chloride but is more environmentally compatible. It is noncar- cinogenic, nonmutagenic, and doesn't bioaccumulate.

When substitution is not possible, ondemand generation may be used to form the toxic chemical. In this scheme less harmful precursors are reacted to form the toxic chemical, which is then fed in real-time directly into a chemical process reactor. The ondemand generation and immediate consumption occurs on the customer's site, eliminating storage and transport of the hazardous substance. Chemical candidates for ondemand generation include vinyl chloride, phosgene, and formaldehyde.

Mitchell and his coworkers Jorge L. Valdes and Gar@ Cadet have developed an elegant ondemand generation process for arsine, an acutely toxic but essential chemical in the fabrication of

electronic devices. Prior to this development, arsine was transported to the manufacturing site in compressed cylinders and then stored until used. Because of the possibility Of sudden accidental releases, the cylinders had to be stored re- motely in specially designed containment facilities. Each such storage facility, Mitchell says. Costs $1 million to build and maintain. AT&T now saves a total of $3 million in construction and maintenance costs because its three storage facilities are no longer needed.

In the ondemand generation of arsine, the reagent is electrochemically synthe- sized at an arsenic metal cathode in an electrolytic cell containing 1N potassium hydroxide. In the electrochemical cell of the commercial ondemand gemerator, a unique packed-bed cathode compartment permits up to 10 Ib of pure arsenic metal to be reduced to arsine. The elec- trode compartment is designed for uni- form current distribution so the cathode material is consumed in a controlled manner yielding arsine at 85%. Hydro- gen formation is minimized--held to 15%:

As + 3H,O + 38- - ASH, + 3OH- 2H,O + 28- - H, +20H-

Other components of the generator include two drying columns and automated pressure and flow-regulation controls. The entire system, housed in a standard toxic-gas cabinet, is controlled by a direct-cwent power supply and a micro- processor. The generator has been inter- faced with appropriate reactors to form GaAs and InGaAs materials that contained fewer impurities than those formed using cylinder-stored arsine.

Mitchell's lab is now working on ondemand generators for phosphine and silane. Along with arsine, these toxic chemicals are "the ones most abundantly used in the production of semiconduo tor devices." Mitchell explains.

Because of these efforts, Mitchell believes that he and his group are contrib- uting to the greening of industry.

cycling, and reclamation [of secondary materials] fits into pollution prevention." Through reuse and recycling a process waste can metamorphose into a process intermediate.

Byers urges a streamlining of the process for permitting reuse, recycling, and reclamation facilities. As it now stands, "RCRA permits are so extensive and ex-

pensive to develop" that many companies forego recycling to cut "all the regulatory hassle required by RCRA," 3M's Zosel explains.

Even accounting practices have become obstacles to preventing emissions. As EPA's Atcheson says, there are two main problems with current accounting methods. "One, they don't account for many potential envi-

July 8. 1991 CXEN 15

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Atcheson (above), McLemore: need to overcome barrien to pollution

prevention

ronmental costs such as bad public relations, long-term liability, or future regulatory changes. And two, the ability to apply an environmental compliance cost to a specific product or process is not typical in industry. Usually environmental costs are aggregated in the overhead function."

Because the linkage between an emission and a specific process line is not made, an avoidance cost can't be calculated. "You really don't know whether it's in your interest to do pollution prevention," Atcheson says. However, the Toxics Release Inventory is making it easier for industry to make the link.

EPA has a model accounting approach, the "Pollu- tion Prevention Benefits Manual," that allows for these environmental externals. Ronald T. McHugh, an EPA economist, says the manual is an important step forward because as "a living document" i t allows for changes in the regulatory framework.

Atcheson believes that some European countries, the Netherlands for example, may have slight different accounting procedures that require companies to list their environmental liabilities separately. This seemingly simple change would then allow companies to make both financial decisions and environmental ones.

Still another barrier to pollution prevention is education. Until recently, Ethyl's manager for regulatory affairs, Paula C. McLemore, says, "Most engineers were challenged to make a product work, not to minimize pollution." There is still no emphasis on pollution prevention in the educational arena, she says, and she is not merely focusing on educating engineers. Business school students- future business managers-also need to have the pollution prevention ethic instilled in them.

"I don't sense much of a change in educating today's

16 July 8. 1991 CBEN

engineers," says Henry A. McCee, director of the National Science Foundation's chemical and thermal systems division. "Chemical engineering curricula are already jam-packed full," he says, and this may be part of the reason they do not yet incorporate pollution prevention.

One of the new activities for McGee's division "is a venture we're putting together with the Council for Chemical Re- search designed to stimulate more research and teaching on environmentally benign manufacturing." NSF may formal- ly announce this venture in late summer. And once funding is obtained, the Na- tional Academy of Sciences' Board on Chemical Sciences & Technology will undertake a study that in part will delineate pollution prevention opportunities in chemistry and chemical engineering.

Along parallel lines, OTA is now con- ducting a study requested by Rep. Brown and Rep. John D. Dingell (D.-Mich.), chairman of the House Energy & Com- merce Committee, the working title of which is "Integrating Product Design with Environmental Goals." It will in-

clude, among others, chapters on household chemicals and new materials. Project director Gregory Eyring expects the study to be published as early as next Febru- ary.

So why is pollution prevention the environmental issue of the day? To paraphrase, how you answer depends on where you sit.

Deeohn Ferris, director of the National Wildlife Fed- eration's environmental quality division, believes, "It's not so much a change of attitude, but a recognition that we can't continue to squander our resources. The public is not going to accept the level of pollution industry has been spewing forth. And there is a nascent recognition by industry of this." CMAs Mason cites the Toxics Release Inventory as a

major impetus for reducing wastes. And McLemore ticks off refocused EPA goals that allow for more integration of activities, "the environmental awareness of the eighties, and companies' belief that they need to be more responsible" as reasons for the current emphasis on prevention. But she has another thought: "There's a balance among the environment, energy, and the econ- omv. The economy and energy are now more stable, so this allows us to pull the environmental picture more tightly in line with the other two."

The straightforward answer may be that it is simply logical from a social point of view. But it is not an endpoint. As Eyring notes, "The real issue we have to face is go-

ing beyond pollution prevention. Prevention is about efficiency, which won't necessarily get us the sustainable environmental quality we want." And for that endpoint, the measures of success are such key environmental vari- ables as thriving rain forests, global biodiversity, and decreased carbon dioxide emissions.

87 4 9e

SUPERCRITICAL CARBON DIOXIDE IN CHEMICAL PROCESSES

Grahame A. Leach

FOR PRESENTATION AT

AlChE Spring National Meeting

Houston, Texas, Apr i l 7 - 1 1 , 1991

Copyright 0 Author(s)/ Employer(s)

AlChE shal l not be responsible f o r statements o r opinions contained in papers or printed in i t s publications.

SUPKRQUTICAL CARBON DIOHDB IN CHBl4ICA.L PROCBSSBS +Ye

Grahame A. Leach I I A N U SLR; TT f - _ I -c -

Airco Gases 575 Mountain Avenue

Murray Hill, NJ. 07974 MA tt I L i q ;

Liquid and supercritical carbon dioxide is increasingly being used in the chemical industry as a solvent. These uses include the extraction of organics, an alternative cleaning solvent, polymer processing and polymer foaming and as a solvent for crystallization / purification.

With increasing pressures to eliminate the use of chlorofluorocarbons in the chemical of supercritical carbon dioxide achieved vide acceptance.

Host people are avare of the importance of solvents in chemical processes, as a reaction medium or as a means of purification. Hany are also avare of the groving environmental and political pressures in force today vhich look to strongly l i d t the use of conventional solvents. Carbon dioxide, either in the liquid phase or the supercritical phase, is increasingly being used as a safe alternative (L,2,3). In the supercritical phase, carbon dioxide has the solvent properties of a liqaid yet the transport properties of a gas (see table 1).

The criiical point for carbon dioxide is 31.1 C and 7383 kPa abs. At lover temperatures, carbon dioxide can exist as a liquid but on18 as lov as the triple point of -56.6 C, 519 kPa abs. The relatively lov critical temperature means that supercritical carbon dioxide can be used in food extraction without thermally degrading the foodstuff. The initial commercial development of supercritical fluid extraction using carbon dioxide vas in the food industry, primarily decaf- feination, hop extraction and herbslspices extraction. Development vork still continues in the €ood sector (4). -

tndustry, the application as an alternative has

In addition to the low critical temperature, carbon dioxide is nonflammable and its inerting properties help to prevent potential fire hazards. It is also non-toxic. A major use of carbon dioxide is the "fizz" in soda or beer carbonation.

In both of these tvo phases (liquid or supercritical), carbon dioxide is a good solvent for dissolving organic, non-polar chemical s. As the pressure and temperature increase, driving the carbon dioxide from liquid to supercritical, the solvent pover increases. Often the optimum process conditions are a balance between the costs of a high pressure system utilizing high solubility or a lov pressure system with lover solubilities. Host of the extraction systems are closed loop systems. The carbon dioxide is pressurized up to the high (extraction) pressure, is then passed through the extraction vessel, has the pressure lovered in the separation vessel(s) to drop out the extract(s) and is then recirculated by compressing back up to the upper pressure. A small amount of make-up is usually needed in these systems . As previously mentioned, the initial commercial developments were in the

food sector. Hovever, there are nov many applications either in use or under development in the industrial sector. In chemical vaste treatment, liquid carbon dioxide can be used in a countercurrent fluid-fluid extraction system. Contaminated vastevater can have the organics stripped out ( 5 , 6 ) . This technology vas developed by-CrF. Systems. It is also possible to use supercritical carbon dioxide to clean up contaminated soils. Tvo separate studies ( 7 , 8 ) have shovn that supercritical cir6on dioxide can be used to remove pollutants such as DDT or PCB. The U.S. Environmental Protection Agency has supported both of the studies.

As CFC's come under increasing attack and are being phased out, plastics processors have a problem finding alternative bloving agents for polymer foaming. Supercritical carbon dioxide can be used to partially or completely replace the CFC's used in extrusion processes. The carbon dioxide is

cally 35 HPa, into the extruder with the molten polymer resin. After mixing and extrusion, the pressure

* release causes the carbon dioxide to expand and foam the plastic (9). - The U n + p Carbide Corp. developed the UNICARB process vhich can replace much of the volatile organic compounds (VOC's) used in paint spraying and other coating sprays (10). Again, the carbon dioxide is pressurized up to the supercritical state to fully exploit its solvent properties. The VOC emissions can be reduced by as much as 70%. An added advantage is that the coating finish is better than that using conventional solvents. Commercial demonstrations in place right nov are shoving good results.

i injected under high pressure, typi-

The inert properties of carbon dioxide have been utilized in aerogel production. Thermalux in California produce silica aerogels from alcohol solutions (E). To drive off the alcohol after formation of the aerogel, carbon dioxide is used as a

displacing solvent. Having safely removed the alcohol, the liquid carbon dioxide can be vented off without fire risks.

There are also other areas under development. Liquid or supercritical carbon dioxide can be used as a cleaning solvent, replacing solvents such as CFCIs, methylene chloride or l,l,l-trichloroethane (methyl chloro -form) ( 1 2 , 1 3 , 2 , 5 l 3 * There appears to be big potential in replacing vapor degreesing and even dry cleaning!

Carbon dioxide .can also be used in purification processes. This can be either stripping impurities out of a process, e.g. the removal of unreacted monomers, oligomers and by-products from polymers (17). It can also be used as a solvent from vhich the desired product can be crystallized in a pure fcrm. The latter has a great potential in the pharmaceutical or fine chemicals industry (18). There have also been studies v h G h shov the use of supercritical carbon dioxide as a reaction medium, especially enzymat- ic reactions (2,3,19). - - -

Table 1. Orders of magnitude of physical data for various phases.

Phase Density Diffusion Viscosity

(kg/m3) (m2/s) (kg1m.s)

Gas 10

S.C. 300

Literature Cited

1. J.H.L. Penninger, H.Radosz, M . A . McRugh 6 V.J. Krukonis (Eds.), "Supercritical Fluid Technology", Process Technology Proceedings 3, Elsevier Science, Nev York NY, 1985.

. I . . \

2. H.A. HcHugh 6 V.J. Krukonis, "Supercritical Fluid Extraction", Buttervorth Publishers, Stoneham HA, 1986.

3. K.P. Johnston 6 J.H.L. Penninger (Eds), "Supercritical Fluid Science and Technology", ACS Symposium Series 406, 1989.

4 . Proceedings of the IBC Conference "Fat and Cholesterol Reduced Foods", Harch 22-24 1990, Nev Orleans LA.

5. W.E. HcGovern 6 P.N. Rice, "Critical Fluid Extraction Treatment of Organic Wastevater", Pollution Engineering Magazine, September 1988.

6. Yeo, S.D. 6 Akgerman, A., "Supercritical Extraction of Organic Mixtures from Aqueous Solutions", AIChE Journal, 1990, - 36(11), 1743-1747.

11. "Aerngels : Solid Pieces of t!-tt..lng", Compressed Air Hagazine, 3Jble 1989, 27-31.

12. "Cleaning vith Supercritical Carbon Dioxide" NASA Report HSF-29611

13. Proceedings of the USAFIDOE International Workshop on Solvent Substitution, Dec 4-7 1990, Phoenix A?,.

14. W.K. Tolley, P.B. Altringer 6 D.C. Seidel, "Stripping Organics from Hetal and Mineral Surfaces using Supercritical Fluids", U.S. Dept. of the Interior, Bureau of Hines publication.

15. W.K. Tolley, P.B. Altringer, S.R. Crane 6 D.C. Seidel "Supercritical Fluid Extraction Apparatus for the veta1 Processing Laboratory", U.S. Dept. of the Interior, Bureau of Hines publication.

7. K.H. Dooley, D. Ghonasgf, F.C. 16. D.P. Jackson, "Dense Phase Carbon Knopf 6 R.P. Gambrell, Dioxide Cleaning Process", Tenth "Supercri t ical CO -Cosolvent Extraction of Confaminated Soils and Sediments", Environmental Danvers HA. Progress, 1990, - 9(4), 197-203.

Kosson, "Supercritical Fluid ChemTech, December 1987, 750-757. Extraction of Aromatic Contaminants from a Sandy Loam 18. K.A. Larson 6 H.L. King, Soil", Environmental Progress, "Evaluation of Supercritical Fluid 1990, 9(4), 204-210. Extraction in the Pharmaceutical

Industry", Biotechnology Progress,

Contamination Control Working Group Meeting, Hay 15 1987,

17. K.H. Scholsky, "Process Polymers 8. A.T. Andrevs, R.C. Ahlert 6 D . S . vith Supercritical Fluids",

- 9. L.H. Zvolinski & Frank J. Dwyer, 1986, - 2(2),73-82.

"Dual Bloving Agents Lover Cost of Polystyrene Foams", Plastics 19. B. Subramaniam 6 H.A. HcHugh, Engineering, 1986, - 42(5), 45-48. "Reactions in Supercritical

A.C. Kuo, C. Lee, K.A. Nielsen, "Supercritical Fluid Spray Application Technology : A Pollution Prevention Technology for the Future", Water-Borne 6 Higher-Solids Coatings Symposium, February 21-23, 1990.

Fluids", Ind. Eng. Chem. Process 10. D.C. Busby, C.V. Zlancy, K.L. Hoy, Des. Dev., 1986, - 25(1), 1-12.

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