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Manufacturing of Cumene
Gharda institute of technology, lavel Page 1
Chapter 1
INTRODUCTION
Cumene is the common name for isopropyl benzene, an organic compound that is an
aromatic hydrocarbon. It is a constituent of crude oil and refined fuels. It is a flammable
colorless liquid that has a boiling point of 152 C. Nearly all the cumene that is produced as a
pure compound on an industrial scale is converted to cumene hydro-peroxide, which is an
intermediate in the synthesis of other industrially important chemicals such as phenol and
acetone.
Cumene (isopropyl benzene) is produced by reacting propylene and benzene over an
acid catalyst. Cumene may be used to increase the octane in gasoline, but its primary use is as a
feedstock for manufacturing phenol and acetone. The preparation of cumene was first described
in 1841 when Gerhardt and Cahours obtained it by distilling cumic acid with lime. The use of
aluminium chloride to alkylate benzene was reported by Radziewanowski in 1892. Before the
development of the cumene route to phenol and acetone, cumene had been used extensively
during World War II as a fuel additive to improve the performance of aircraft piston engines.
Like phenol and acetone, -methylstyrene, diisopropylbenzene, or acetophenone, although these
cumene derivative compounds are of considerable commercial importance. Currently, over 80%
of all cumene is produced by using zeolite based processes. Early processes using zeolite based
catalyst system were developed in the late 1980s.[9]
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Chapter 2
PROPERTIES
Cumene is colorless liquid soluble in alcohol, carbon tetra chloride, ether and benzene. It
is insoluble in water.
2.1 PHYSICAL PROPERTIES OF CUMENE[8]
PROPERTY VALUE
Molecular weight 120.19
Boiling Point, C 152.39
Freezing point, C -96.03
Density, gm/cm3
0C
20C
40C
0.8786
0.8169
0.8450
Thermal conductivity, w/m.k
25C
0.124
Viscosity, mPa.s (cp)
0C
20C
40C
1.076
0.791
0.612
Surface tension, mN/m
20C
0.791
Flash point, C 44
Autoignition temperature, C 523
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Antoine Constants
A
B
C
13.99
3400
207.78
2.2 THERMODYNAMIC PROPERTIES OF CUMENE[8]
PROPERTY VALUE
Relative molar mass 120.2
Critical temperature, C 351.4
Critical pressure, Kpa 3220
Critical density, g/cm3 0.280
Heat of vapourisation at bp, J/g 312
Heat of vapourisation at 25C, J/g 367
2.3 CHEMICAL PROPERTIES:[8]
1. Cumene undergoes oxidation t o give cumene hydroperoxide by means of air or
Oxygen
C6H5CH(CH3)2 + O2 C6H5C(CH3)2OOH
Cumene Oxygen Cumene Hydroperoxide
2. By the catalytic action of dilute sulphuric acid, cumene hydroperoxide is split into
Phenol and acetone
C6H5C(CH3)2OOH C6H5OH + CH3COCH3
Cumene Hydroperoxide Phenol Acetone
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Chapter 3
USES
Cumene is used[2]
1. As feedback for the production of Phenol and its co-product acetone
2. The cumene oxidation process for phenol synthesis has been growing in popularity
Since the 1960s and is prominent today. The first step of this process is the formation
of cumene hydroperoxide. The hydroperoxide is then selectively cleaved to Phenol
and acetone.
3. Phenol in its various for maldehyde resins to bond construction materials like plywood
and composition board (40% o f the phenol produced) for the bisphenol. A employed
in making epoxy resins and polycarbonate (30%) and for caprolactum, the starting
material for nylon-6 (20%). Minor amounts are used for alkylphenols and
pharmaceuticals.
4. The largest use for acetone is in solvents although increasing amounts are used to
make bisphenol A and methylacrylate.
5. Methylstyrene is produced in controlled quantities from the cleavage of cumene
Hydroperoxide or it can be made directly by the dehydrogenation o f cumene.
6. Cumene in minor amounts is used as a thinner for paints, enamels and lacquers and to
produce acetophenone, the chemical intermediate dicumylperoxide and diisopropyl
benzene.
7. Cumene is also used as a solvent for fats and raisins.
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Chapter 4
MANUFACTURING PROCESSES OF CUMENE.
There are four types of manufacturing process of cumene.
1. Liquid phase alkylation using Phosphoric acid.
2. Liquid phase alkylation using Aluminium chloride.
3. Q-Max process.
4. CD-Cumene process.
4.1 LIQUID PHASE ALKYLATION USING PHOSPHORIC ACID [2]
4.1.1 INTRODUCTION
SPA (Solid phosphoric acid) remains a viable catalyst for cumene syenthesis. In recent
years , producers have been given increasing incentives for better cumene product quality of the
phenol, acetone, and especially alpha-methyl styrene produced from the downstream phenol
units.
4.1.2 CHEMICAL REACTION
Main Reaction
C6H6 + CH3.CH=CH2 C6H5. C3H7 ;
Side Reaction
C6 H6 + nCH3CH=CH2 C6 H6-n.(CH)n
4.1.3 PROCESS DESCRIPTION
Propylene-propane feedstock from refinery off gases from a naphtha steam cracking
plant and recycle benzene is mixed with benzene are charged upflow into fixed bed reactor,
which operates at 3-4 MPa and at 200-260 C and pumped at 25 atms. Into the top of a reactor
packed stage wise with H3PO4 impregnated catalyst. The SPA catalyst provides an essentially
complete conversion of propylene on a one pass basis. The temperature is maintained at
approximately 250 C by adding cold propane at each stage to absorb heat of reaction.
The reactor effluent is depropanized and the propane split into quench or product streams.
The propanized bottoms are separated into benzene, cumene,and polycumenes in the remaining
Jie_ShengHighlight
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two stills. A typical reactor effluent stream contain 94.8 wt% cumene and 3.1 wt%
diisopropylbenzene (DIPB). The remaining 2.1% is primarily heavy aromatics. This high yield
of cumene is achieved without transalkylation of DIPB is the key advantage of SPA catalyst
process. The cumene product is 99.9 wt% pure. The heave aromatics which have research octane
no (RON) of about 109 can be either used as high octane gasoline blending components or
combined with additional benzene and sent to transalkylation section of the plant where DIPB is
converted to cumene. The overall yield of cumene for this process based on benzene and
propylene is typically 97-98 wt% if transalkylation is included or 94-96 wt% without
transalkylation
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4.1.4 PROCESS FLOW DIAGRAM
Figure 4.1.4.a Liquid phase alkylation using phosphoric acid
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4.2 LIQUID PHASE ALKYLATION USING AlCl3 [2]
4.2.1 INTRODUCTION
Aluminium chloride is a preferred alkylating agent for the production of cumene.
Basically the design is same to that described for other processes, having pretreatment section if
required, a reactor section and a distillation section. The reaction conditions, including
arrangement for the feeding catalyst and recycle of polyalkylbenzenes for dealkylation are
however quite different.
4.2.2 PROCESS DESCRIPTION-
If feed treatment is required depending on the quality of feedstock, propylene is dried in a
regenerative absorptive drier and fed to de-ethanizer where c2 compounds are distilled. The
bottoms pass to a propylene column where c4s and heavier are removed in the base stream.
Liquid propylene in the overheads is vaporized and fed to the reactor. Fresh benzene contains too
much water for immediate addition to the reactors, is mixed with recycle benzene and fed to
column. After condensation, benzene and water separate in a decanter. Benzene from the base
contains less than 10ppm water.
The reaction section usually consists of two or more brick lined vessels partitioned into
reaction and settling zones with downstream separators and wash drums. All the reactants and
recycle streams are introduced into the reaction zone. Since agitation is required, propylene
vapours are admitted at the base where catalyst complex, which is insoluble in a hydrocarbon,
tends to settle. The complex is hereby lifted and mixed intimately with the reactants. Aluminium
chloride is added to the top of the reactor and the promoter usually HCl or isopropyl enters with
the reactant. The promoter is essential for stabilizing the catalyst complex, for only a stable
complex will catalyze the reaction. In addition to the gaseous feed to distribute the catalyst
complex, there may be provided a pump to recirculate settled complex to the top of the reaction
zone and a compressor to recycle propane. The distillation section consist of ethylbenzene unit
have been constructed where the catalyst complex is prepared in a separate vessel. Care has to be
taken with the reactor off gases which in addition to benzene and other light hydrocarbons
contains HCl. The benzene is recovered in an absorber containing recycling PAB and the HCl is
scrubbed out of the off- gas in two towers, one containing water and the other containing caustic
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soda solution. The residual gas can be compressed and used as fuel. The material heavier than
cumene is not disposed of as fuel, is returned to the reactors for transalkylation after removing
the heaviest polyalkylbenzenes. The later operation is conducted in a small column under high
vacuum.
4.2.3 PROCESS FLOW DIAGRAM
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Fig 4.2.3.a Liqid phase alkylation using Aluminium Chloride
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4.3 Q-MAX PROCESS[1,5,6]
4.3.1 INTRODUCTION
The Q- Max process is based on liquid phase process. The Q-Max process produces
nearly equilibrium levels of cumene between 85 to 95 mole% and DIPB between 5 and 15
mole%. The Q-Max process had selected most promising catalyst based on beta zeolite for
cumene production.
4.3.2 PROCESS DESCRIPTION
A Q-max unit consists of an alkylation reactor, a distillation section, and a transalkylation
reactor. Both reactors are fixed bed. The alkylation reactor is divided into four catalyst beds
contained in a single reactor vessel. Propylene and a mixture of fresh and recycle benzene are
charged to the alkylation reactor, where the propylene reacts to completion to form mainly
cumene. Effluent from the alkylation reactor is sent to the depropanized column, which removes
the propane that entered the unit with the propylene feed, along with any excess water which
may have accompanied the feeds. The Depropanizer column bottoms is sent to the benzene
column where benzene is collected overhead and recycled. Benzene column bottom is sent to the
cumene column where cumene product is recovered overhead. The bottom from the cumene
column, containing mostly diisopropylbenzene is sent to the DIPB column where DIPB is
recovered and recycled to the transalkylation reactor. The bottoms from the DIPB column consist
of a small stream of heavy aromatic by-product which are normally used as high octane gasoline
blending component.
The catalyst in both the alkylation and transalkylation reactors is regenerable. The typical
design cycle length between regenerations is 2years, but the unit can be designed for somewhat
longer cycles if desired. Ultimate catalyst life is at least three cycle. Mild operating conditions
and a corrosion free process environment permit the use of carbon steel construction and
conventional process equipment.
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4.3.3 PROCESS FLOW DIAGRAM
Recycle Benzene
Benzene
Propylene
Cumene
DIPB
Heavies
DIPB
Column
Cumene
Column
Benzene
Column
Transalkylation
Reactor Depropanizer
Alkylation
Reactor
Propane
Figure4.3.3.a : Q-Max process
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4.4 CD CUMENE PROCESS[1]
4.4.1 INTRODUCTION
The CD- Cumene process produces ultra high purity cumene using a proprietary zeolite
catalyst that is non corrosive and environmentally friendly.
4.4.2 PROCESS DESCRIPTION
Cumene is formed by the catalytic alkylation of benzene with propylene. CD-cumene
process uses a proprietary zeolite catalyst. The catalyst is non corrosive and environmentally
friendly. This modern process features higher product yields, with a much lower capital
investment, than the environmentally outdated acid- based processes.
The unique catalytic distillation column combines reaction and fractionation in a single
unit operation. The alkylation reaction takes place isothermally and at low temperature. Reaction
products are continuously removed from the reaction zones by distillation. These factors limit the
formation of by-product impurities, enhance product purity and yields, and result in expected
reactor run lengths in excess of two years. Low operating temperatures result in lower equipment
design and operating pressures, which help to decrease capital investment, improve safety of
operations, and minimizing fugitive emissions. All waste heat, including the heat of reaction, is
recovered for improved energy efficiency.
The CD-cumene technology can process chemical or refinery grade propylene. It can also
use dilute propylene streams with purity as low as 10mol percent, provided the content of other
olefins and related impurities are within specification.
ZEOLITE CATALYST.
Except for the CDTech process, which combines catalytic reaction and distillation in a
single column, all zeolite-based processes consist of essentially the same flowsheet
configuration. The alkylation reaction is carried out in fixed-bed reactors at temperatures below
those used in SPA-based processes. When refinerygrade propylene is used as a feedstock, the
effluent from alkylation is sent to a depropanizer column that removes propane overhead. A
separate transalkylation reactor converts recycled PIPB and benzene to additional cumene. The
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bottoms of the depropanizer are then mixed with the transalkylation reactor effluent and fed to a
series of three distillation columns. Benzene, product cumene, and PIPB are respectively
separated in the overhead of each column, with PIPB and benzene recycled to the reaction
system. A small stream of heavy aromatics is separated in the bottoms of the PIPB column. Like
the AlCl3 catalyst, zeolites are sufficiently active to transalkylate PIPB back to cumene. Overall
selectivity of benzene to cumene is quite high, varying from 99.7% to almost stoichiometric,
depending on the nature of the zeolite employed. Product purities as high as 99.97% can be
obtained, with B/P feed ratios between 3 and 5. A particular advantage of the zeolite catalysts is
that they are regenerable and can be used for several cycles. Therefore, the waste disposal
problems associated with SPA and AlCl3 catalysts are greatly reduced. In addition, carbon steel
can be used as the material of construction throughout the plant because of the mild operating
conditions and the absence of highly corrosive compounds. One limitation of the zeolite
technology is potential poisoning of the catalyst by contaminants in the feed.
Depending on feedstock quality, guard beds or additional feed pretreatment may thus be
required. If refinerygrade propylene is used, for example, its sulfur content must be closely
controlled.
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4.4.3 PROCESS FLOW DIAGRAM
PIPB Recycle
Cumene
Cumene Column
PIPB
Column
Heavies
Propane
Benzene
Propylene
Figure : CD- Cumene process
Transalkylator
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Chapter 5
SELECTION OF PROCESS
5.1 ADVANTAGES
5.1.1 LIQUID PHASE ALKYLATION USING PHOSPHORIC ACID[2]
a) The SPA catalyst provides an essentially complete conversion of propylene on a one
pass basis.
b) Cumene product 99.9 wt% pure.
c) By product removal is relatively simple.
5.1.2 LIQUID PHASE ALKYLATION USING AlCl3[2]
a) Propane in propylene feed is recovered as liquid petroleum gas(LPG)
b) By product removal is relatively simple.
c) PAB may be recycled to the reactor as aluminium chloride has ability to
transalkylated PAB in presence of benzene.
5.1.3 Q-MAX PROCESS[1]
a) The catalyst in the both alkylation and Transalkylation reactor are regenerable.
b) The expected catalyst cycle is 2-4 years and the catalyst should not need replacement
for at least 3 cycles.
c) The Q-Max requires minimum pretreatment of feeds, which further minimizes the
capital costs.
5.1.4 CD- CUMENE PROCESS[1]
a) High selectivity and lower by product formation. High product yield; reduced plot
area.
b) Lower maintenance cost.
c) Decrease capital investment; improve safety and operability; applicable to conversion
of existing cumene plants.
d) Reduces utilities and operating cost; recover all waste heat and heat of reactions.
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e) Improves economics plant can be custom designed to process specific feed stocks
including the less expensive feedstock.
f) Continuous process.
g) Meets evolving environmental requirements.
h) Catalytic reaction and distillation is done in single column.
5.2 DISADVANTAGES
5.2.1 LIQUID PHASE ALKYLATION USING PHOSPHORIC ACID[2]
:
a) Cumene yield is limited to 95% because of the oligomerization of propylene and the
formation of heavy alykalate by-products.
b) The process requires a relatively high benzene propylene molar feed ratio on the
order of 7/1 to maintain cumene yield.
c) The catalyst is not regenerable and must be disposed at the end of each short catalyst
cycle.
5.2.2 LIQUID PHASE ALKYLATION USING ALUMINIUM CHLORIDE[2]
:
a) Feed pretreatment is required.
b) The presence of HCL in and around the reaction area can be troublesome; its
treatment is the major disadvantage of this process.
Q-Max Process and CD-Cumene process doesnt have any disadvantage. But from
this two processes CD-Cumene process is more effective than Q-max process because,
a) Extends reactor run length over one year without regeneration, sustain high
conversion and selectivity.
b) Decrease capital investment, improves safety and operability.
c) Reduces utilities and operating costs, recovers all waste heat and heat of reaction.
d) Improves economics- plans can be custom designed to process specific feedstocks
including less expensive feedstock.
So that we are selecting CD-cumene process of manufacturing of CUMENE.
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Chapter 6
THERMODYNAMIC FEASIBILITY
Table 6.a : Thermodynamic data
Component Cp (J/mol k) Entropy
@298(J/mol k)
Hf @298(KJ/mol)
Gf @298(KJ/mol)
Cumene 217.96 388.57 3.93 136.96
Propylene 115.3 266.6 20.42 62.72
Benzene 137.87 269.20 82.93 129.66
Chemical reaction
C3H6 + C6H6 C9H12
Reaction temperature = 170
6.1 Calculation of heat of reaction at 443K
Hr = Hf298 + ( )
{ ( )
+ ( )
}..[10]
Cp values are,[4]
Cp(cumene) = 124.62 + 6.39210-1
T 1.733110-3T2 + 2.214610-6T3
Cp(propylene) = 54.718 + 3.451210-1
T 1.631510-3T2 + 3.875510-6T3
Cp(benzene) = 31.662 + 1.3043T 3.607810-3
T2 + 3.824310
-6T
3
For Cumene
298443 (124.62+6.3293*10-1T-1.7331*10-3T2+2.2146*10-6T3)dT
= 18069.9 + 34002.58 34936.24 + 16956.92
= 34.093 KJ/mol
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For Propylene
298443
(54.718 + 3.4512*10-1
T - 1.6315*10-3
T2
+ 3.8755*10-6
T3)dT
= 7934.11 + 18540.71 32888.16 + 29674.23
= 23.260 KJ/mol
For Benzene
298 353
(-31.662 + 1.3043T 3.6078*10-3T2 + 3.8243*10-6T3)dT +30.75
= 4590.99 + 70070.25 72726.89 + 29282.21 + 30.75
= 22.065KJ/mol
Heat of formation at 298K
Hf298 = Hf(product) Hf(reactant)[10]
= Hf(cumene) [Hf(propylene) +Hf(benzene) ]
= 3.93 (20.42 + 82.93)
= 99.42KJ/mol
Heat of reaction at 443K
Hr443 = 99.42 + 34.093 23.260 22.065
= 110.652KJ/mol
Heat of reaction is negative, so the reaction is exothermic.
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6.2 Calculation of Entropy
S443 = S298 + (
)
..[11]
= S298 + ln(T2/T1) + (T2 T1) { [1/(T2)2] [1/(T1)
2] }
For Cumene
S443 = 388.57 + 124.621 ln(443/298) + 6.3293(443298) +1.733110-3
[ (1/4432) (1/2982) ]
= 388.57 +49.401 + 917.74 1.06810-8
= 1355.711J/mol
For propylene
S443 = 266.6 +54.718 ln(443/298) + 3.451210-1(443298) + 1.631510-3
[ (1/4432) (1/2982) ]
= 266.6 +21.694 +50.04 110-8
= 338.334J/mol
For Benzene
S443 = 269.20 31.662 ln(443/298) + 1.304310^-1(443298) + 3.607810-3
[ (1/4432) (1/2982) ]
= 269.20 12.55 +18.912 2.2210-8
= 275.56J/mol
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Entropy of reaction at 443k
S443 = S(product) S(reactant) [11]
= 1355.711 (338.334 +275.56)
=741.817J/mol
= 741.81710-3
KJ/mol
6.3 calculation of Gibbs free energy
G = H TS [11]
= 110.652 [443(741.81710-3)]
= 439.27KJ/mol
Gibbs free energy is negative, so the reaction is feasible.
6.4 Calculation of equilibrium constant
G = RT ln(Kp) ...... [10]
Kp = (
)
=
= 1.12
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Chapter 7
MATERIAL BALANCE
Plant capacity 300,000 ton / year.
Assuming 300 working days.
Basis- 1000 ton/ day cumene production
= 41666.67 kg/hr
= 346.67 kmol/hr
Reaction-
Main reaction:
C3H6 + C6H6 C9H12
Side reaction:
C9H12 + C3H6 C6H4( CH (CH3)2)2
Assuming 95% conversion is possible in reactor-1. Hence 90% of cumene get converted into
cumene and 5% propylene get reacted with cumene to form PIPB.
Propylene fed = 346.67 kmol/hr
Benzene to propylene feed ratio is 4:1.
Benzene fed = 1400 kmol/hr
Propylene reacted = 0.95 * 346.67
= 329.33 kmol/hr
Unreacted propylene = 346.67 329.33
= 17.34 kmol/hr
Benzene reacted = 0.9 * 346.67
= 312 kmol/hr
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Since the reaction is exothermic.
Hence heat evolved in CD-column is
= 0.95 * propylene feed * heat of reaction
= 0.95 * 346.67 * 96.428
= 31757.26 kJ
Benzene evaporated = (total heat evolved) / (latent heat of benzene)
= (31757.26) / (30.75)
= 1032.75 kmol
Benzene fed into CD-column = benzene evaporated in CD-column + benzene reacted
= 1032.75 + 312
= 1344.75 kmol/hr
Unreacted benzene = 1344.75 312
= 1032.75 kmol/hr
Cumene produced = 312kmol/hr
But 5% of propylene reacts with the cumene and produce PIPB (it contains DIPB and little
amount of TIPB)
Cumene produced = 312 0.05 * 346.67
= 294.67 kmol/hr
Cumene produced in finishing reactor = 0.05 * 346.67
= 17.33 kmol/hr
From given,
Selectivity of propylene to cumene = 81.7
Benzene reacted with DIPB to produce cumene = 0.05 * 346.67
= 17.33 kmol/hr
DIPB produced = 0.98 * 17.33
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= 16.98 kmol/hr
Net amount cumene produced = 312 + 17.33 + 16.98
= 346.31kmol/hr
PIPB produced = 0.02 * 17.33
= 0.3466 kmol/hr
Material balance of cumene column: cumene 346.31 Kmol/hr
Cumene + DIPB
346.31 Kmol/hr + 17.33 Kmol/hr
DIPB 17.33 Kmol/hr
Material balance of DIPB column:
DIPB 16.9834 Kmol/hr
DIPB
17.33 Kmol/hr
Heavy ends
0.3466 Kmol/hr
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Material balance of transalkylation reactor:
Cumene 16.9834Kmol/hr
Benzene + PIPB
16.9834 Kmol/hr +16.9834Kmol/hr
Material balance for finishing reactor:
Benzene = 17.33 kmol/hr
cumene = 17.33 kmol/hr
propylene = 17.33 kmol/hr
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Chapter 8
ENERGY BALANCE
Plant capacity is 300,000 ton / year. Assuming 300 working day .
Basis = 1000 ton of cumene per day
= 346.67 kmol/hr
Cp values data:
Component A B C D
Cumene 10.149 5.1138E-1 -1.7703E-5 -2.2612E-7
Propylene 31.298 7.2449E-1 1.9481E-4 -2.1582E-7
Benzene -31.368 4.7460E-1 -3.1137E-4 8.5237E-8
Energy balance on CD-column
Benzene unreacted benzene + propylene
propylene cumene + PIPB
Cumene synthesis is exothermic reaction.
The heat given out when 1mol propylene reacted is the heat of reaction = 96.428 kJ
Hence total heat given out = 33393.98 kJ/hr
This amount of heat is taken out of reaction zone by evaporation of benzene. This vapour phase
benzene is then cooled and bring to liquid phase. Hence heat taken out in condenser is,
Condenser load = 33393.98 kJ/hr
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Energy balance on cumene column
: Cumene
Cumene + DIPB
DIPB
The cumene with PIPB comes out from CD-column at 152 C. This mixture is heated to near
about 170 C to distill out cumene from the PIPB column.
Heat load on reboiler = mCpT
= [346.67 * 217.96 * (170-152)] + [17.33 * 382.42 * (170-152)]
= 1477.96 * 103 kJ/hr
The cumene is cooled to liquid phase,
Load on condenser = mCp(35-170)
= 346.67 * 217.96 * (35-170)
= 10200.63 * 103 kJ/hr
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Energy balance on PIPB column-
DIPB
DIPB
Heavy ends
PIPB comes out from cumene column is separated in DIPB and heavier ends, for this separation
mixture is heated to 200 c.
Reboiler load = 17.33 * 382.42 * (200-170)
= 1988.35 * 102 kJ/hr
Energy balance on transalkylation reactor-
Cumene
Benzene + PIPB
In this unit producing cumene from DIPB and benzene. Since reaction is exothermic.
The net heat given out from the reaction = 96.428 * 17.33
= 1671.09 kJ/hr
Condenser load = 1671.09 kJ/hr
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Chapter 9
DESIGN OF MULTICOMPONENT DISTILLATION COLUMN
Assume 99% benzene is separated as a overhead & 99.5% cumene is separated as bottom
product
In our case
1. Propylene lighter than light key
2. Benzene light key
3. Cumene heavy key
4. PIPB heavier than heavy key
Material balance
Component Feed Distllate Bottom
Moles Mol.
Fraction
Mol Mol
fraction
Mol Mol
fraction
Propylene 17.34 0.0123 17.34 0.0166 - -
Benzene 1032.75 0.721 1022.42 0.98 10.33 0.0277
Cumene 346.31 0.245 1.732 0..166 344.58 0.926
DIPB 17.33 0.0122 - - 17.33 0.0465
Total 1413.73 372.24
Vapor pressure data
Log p = A- B/(T+C)
Calculation of top temperature
Component yi pi ki xi = yi/ki
Propylene 0.0166 31627.13 17.15 0.000968
Benzene 0.98 927.68 1 0.98
Cumene 0.00166 96.31 0.09 0.018
0.999
Top temperature = 870C
Manufacturing of Cumene
Gharda institute of technology, lavel Page 30
Calculation of bottom temperature
Component Xi Pi ki yi = kixi
Propylene 0.0277 4521.18 5.43 0.150411
Benzene 0.926 733.30 0.9 0.8334
Cumene 0.0465 185.11 0.188 0.008742
0.993
Bottom temp = 152 0
C
Nmin = (
) (
)
= (
)(
)
= 3.67
Minimum reflux ratio
Lower pinch temperature = column top temp. +
(temp. of bottom- temp of top)
= 87 +
(152-87)
= 130.33
Upper pinch temperature = column top temp. +
(temp. of bottom- temp of top)
= 87 +
(152-87)
= 108.67
Component Vapour
pressure at
108.67
i Vapour pressure at
130.33
i avg
Propylene 45881.14 219.17 64840.97 158.53 186.4
Benzene 1684.86 8.05 2865.66 7.0 7.51
Cumene 209.34 1.0 409.01 1.0 1.0
DIPB 38.91 0.186 89.26 0.218 0.2
Manufacturing of Cumene
Gharda institute of technology, lavel Page 31
The minimum reflux ratio can be calculated by underwoods method
RRmin + 1 =
for all component.
= 1 q
The feed line is a saturated liquid at its boiling point, so q = 1.
By trial and error method,
lies between, B < < A
A = 7.51 B = 1
1 < < 7.51
Trial and error method
L.H.S R.H.S = L.H.S R.H.S
7 10.58 0.000358 10.579642
5 2.1 0.000508 2.099492
1.2 -0.354 0.00244 -0.356
2 0.749 0.001355 0.74
1.5 0.423 0.00187 0.421
R Rmin = 0.238
Assume,
= 1.5
R = 1.5 * 0.238
= 0.367
= (0.238/1.238)
= 0.2
= (0.36/1.36)
= 0.264
Manufacturing of Cumene
Gharda institute of technology, lavel Page 32
From, fig.9.4, Erbar Maddox correlation (
vs
)
= 0.38
N =
= 9.66
= 10
Assuming 50 % efficiency of stages
Theoretical no of stages =
= 20
The Principal factor that determine the tower diameter is the gas ( vapour) velocity. It
is the flooding condition that fixes the upper limit of gas ( vapour) velocity. The flooding
velocity is given by
vfl = (
)0.5
Where Vfl = flooding velocity of gas ( vapour )
K = constant
l , v = density of liquid & vapour respectively
here , = 2.7 Kg/ m3
= 862 Kg/ m3
Assuming plate spacing 0.45m
from fig 9.1 K = 0.08
vfl = 1.42 m/s.
Assuming 85% flooding condition
Vfl = 0.85 1.42
= 1.21 m/s.
Manufacturing of Cumene
Gharda institute of technology, lavel Page 33
Maximum flow rate
Vmax
=
= 8.36 m/s
Net area required = An
=
=
= 5.88 m2.
An = At Ad
= At 0.12At
= 0.88At
At =
= 6.68 m2
Column diameter
Dt =
=
= 2.91 m
Manufacturing of Cumene
Gharda institute of technology, lavel Page 34
LIQUID FLOW PATTERN:
Liquid flow pattern is determined by two parameters
1. Maximum liquid flowrate
2. Column diameter
Here , Lmax =
= 0.0238 m3/s
Hole area, Ah = 10% of active area
Aa = At 2Ad
= 6.68 2 0.80
= 5.08 m2
Ah = 0.10 5.08
= 0.508 m2
Weir length = 0.77 Dt
= 0.77 2.91
= 2.24 m
Lets take
Hole diameter = 7 mm
Plate thickness= 5 mm
Manufacturing of Cumene
Gharda institute of technology, lavel Page 35
PLATE DESIGN:
Column diameter = 2.91 m
Column cross section ,
At = 6.68 m2
Weir Height :
Since column operating at pressure above atmospheric pressure,
hw = 50 mm
Plate thickness = 5 mm
CROSS CHECK:( FOR PLATE DIMENSIONS)
Maximum Liquid rate = 23.12 kg/s
Assuming turndown ratio at 70% of maximum liquid flowrate ,
so that minimum liquid flowrate =
*23.12 =16.184 kg/s.
The height of liquid crest over the segmental weir:
(how)max = 0.70 (
)(2/3)
= 36 mm of clear liquid
(how)min = 0.75 (
)(2/3)
= 30 mm of clear liquid
At minimum flowrate, dh
hw + how = 50+30=80 mm
Manufacturing of Cumene
Gharda institute of technology, lavel Page 36
from fig 9.2, Kw = 30.2
therefore minimum vapour velocity,
vmin =
( ( ))
vmin =
( ( ))
= 7.20 m/s
But actual vapour velocity
=
=
= 9.92 m/s.
Thus the minimum operating velocity (9.92 m/s) lies well above the weep point (i.e. when
vapour velocity = 7.20 m/s)
Therefore our design is safe from operating point of view
Plate pressure drop :
The total plate pressure drop is given by,
ht = hd + hl + hr
dry plate drop
hd = K1+ K2 (vgh)2 (
)
for sieve plate ,
K1=0,
K2=
Manufacturing of Cumene
Gharda institute of technology, lavel Page 37
Discharge coefficient Cv is determined as follows,
From fig.9.3, Cv= 0.765
Velocity through holes
Vgh =
hd = 50.85*10-3 (
) (
)
= 3.42 mm of clear liquid
Pressure drop due to staric liquid head,
hl = hw + how
= 50+36
= 86 mm of clear liquid
Residual head,
hr =
=
= 14 mm of clear liquid
The total pressure drop
ht = hd + hl + hr
= 3.42 + 86 + 14
= 103.42 mm of clear liquid
Manufacturing of Cumene
Gharda institute of technology, lavel Page 38
Downcomer area backup :
Backup in downcomer is given by,
Hdc = ht + hw + how + hda
Head loss in the downcomer due to liquid flow under the downcomer apron :
hda = 0.166*(
)
now,
Aap = hap*lw
Hap= height of lower edge of the apron above the tray
= hw 10 = 50 10 =40 mm
Lw = 2.24 m
Aap = Area under the downcomer apron
= 0.04 * 2.24
= 0.0896 m2
Since Aap < Ad we take Ad as Am
hda = 0.166 (
)2
= 1.12 mm of clear liquid
Hdc = 103.42+ 50 +36 + 1.12
= 190.54 mm of clear liquid
Manufacturing of Cumene
Gharda institute of technology, lavel Page 39
Check :
To avoid flooding :
Hdc <
( )
Now ,
( )
( )
Since hdc < 0.250m ,so there will be no flooding at specified operating condition that means tray
spacing is acceptable.
Residence time :
r =
=
= 5.68 s.
Total height of tower
= [no of plates * tray spacing] + clearance at top + clearance at bottom
= [20 * 0.5] + 0.5 + 0.5
= 10 m
So the design is satisfactory.
Manufacturing of Cumene
Gharda institute of technology, lavel Page 40
SHELL THICKNESS :
For thickness of shell of distillation column we required following data,
1. Design Pressure, P = 1.1 * operating pressure
= 1.1 * 2.757
= 3.0327 N/mm2
2. Permissible tensile stress, f = 95 N/mm2 ( MOC= CARBON STEEL)
3. Joint efficiency facor , J = 0.85
4. Inner diameter, Di =2.91 m
5. Corrosion allowance, C = 1.5 mm
Shell thickness is given by,
ts=
ts =
ts = 57.19 mm
Head thickness :
for safety we use hemispherical head at top & bottom of distillation column. The head
thickness is given by ,
th =
th =
th = 23 mm
Manufacturing of Cumene
Gharda institute of technology, lavel Page 41
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Gharda institute of technology, lavel Page 42
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Gharda institute of technology, lavel Page 43
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Gharda institute of technology, lavel Page 44
Manufacturing of Cumene
Gharda institute of technology, lavel Page 45
Chapter 10
COST ESTIMATION
Cost of cumene plant of capacity 400 TPD in 1990 is Rs.23.4107
Therefore cost of 1000 TPD in 1990 is:
C1 = C2 (Q1/Q2)0.6
= 23.4 x 107(1000/400)
0.6
= Rs.4.055 x 108
Chemical Engineering Plant Cost Index:
Cost index in 1990 = 357.6
Cost index in 2010 = 539.1
Thus, Present cost of Plant = (original cost) (present cost index)/(past cost index)
= (4.055 x 108) (539.1/357.6)
= Rs. 6.113108
Fixed Capital Cost (FCI) = Rs. 6.113108
Estimation of Capital Investment Cost:
I. Direct Costs: material and labour involved in actual installation of complete facility (70-85%
of fixed-capital investment)
a) Equipment + installation + instrumentation + piping + electrical + insulation + painting (50-
60% of Fixed-capital investment)
1. Purchased equipment cost (PEC): (15-40% of Fixed-capital investment)
Consider purchased equipment cost = 25% of Fixed-capital investment
PEC = 25% of 6.113108
= 0.25 6.113108
= Rs. 1.528108
2. Installation, including insulation and painting: (25-55% of purchased equipment cost.)
Consider the Installation cost = 40% of Purchased equipment cost
Manufacturing of Cumene
Gharda institute of technology, lavel Page 46
= 40% of 1.528108
= 0.40 1.528108
= Rs.0.611210
8
3. Instrumentation and controls, installed: (6-30% of Purchased equipment cost.)
Consider the installation cost = 20% of Purchased equipment cost
= 20% of 1.528x108
= 0.20 1.528108
= Rs. 0.3056108
4. Piping installed: (10-80% of Purchased equipment cost)
Consider the piping cost = 40% Purchased equipment cost
= 0.40 1.528108
= Rs. 0.6112108
5. Electrical, installed: (10-40% of Purchased equipment cost)
Consider Electrical cost = 25% of Purchased equipment cost
= 25% of 1.528 108
= 0.25 1.528108
= Rs.0.382108
B. Buildings, process and Auxiliary: (10-70% of Purchased equipment cost
Consider Buildings, process and auxiliary cost,
= 40% of PEC
= 40% of 1.528 108
= 0.40 1.528108
= Rs. 0.6112108
Manufacturing of Cumene
Gharda institute of technology, lavel Page 47
C. Service facilities and yard improvements: (40-100% of Purchased equipment cost)
Consider the cost of service facilities and yard improvement,
= 60% of PEC
= 60% of 1.528 108
= 0.60 1.52810
8
= Rs. 0.916810
8
D. Land: (1-2% of fixed capital investment or 4-8% of Purchased equipment cost)
Consider the cost of land = 6% PEC
= 6% of 1.528 108
= 0.06 1.528108
= Rs. 0.0916810
8
Thus, Direct cost = Rs. 5.058108 ----- (82.74% of FCI)
II. Indirect costs: expenses which are not directly involved with material and labour of actual
installation of complete facility (15-30% of Fixed-capital investment)
A. Engineering and Supervision: (5-30% of direct costs)
Consider the cost of engineering and supervision,
= 10% of Direct costs
= 10% of 5.058 108
= 0.1 5.058 108
= Rs.0.5058108
B. Construction Expense and Contractors fee: (6-30% of direct costs)
Consider the construction expense and contractors fee,
= 10% of Direct costs
= 10% of 5.058108
= 0.1 5.058 108
Manufacturing of Cumene
Gharda institute of technology, lavel Page 48
= 0.505810
8
C. Contingency: (5-15% of Fixed-capital investment)
Consider the contingency cost = 10% of Fixed-capital investment
= 12% of 6.113108
= 0.12 6.113108
= Rs. 0.7336108
Thus, Indirect Costs = Rs. 1.7452108 --- (28.55% of FCI)
III. Fixed Capital Investment:
Fixed capital investment = Direct costs + Indirect costs
= (5.058108) + (1.745210
8)
= Rs. 6.803108
IV. Working Capital: (10-20% of Fixed-capital investment)
Consider the Working Capital = 15% of Fixed-capital investment.
= 15% of 6.803108
= 0.15 6.803108
= Rs. 1.020510
8
V. Total Capital Investment (TCI):
Total capital investment = Fixed capital investment + Working capital
= (6.803108) + (1.020510
8)
= Rs. 7.8235108
Estimation of Total Product cost:
I. Manufacturing Cost = Direct production cost + Fixed charges + Plant overhead cost.
A. Fixed Charges: (10-20% total product cost)
i. Depreciation: (13% of FCI for machinery and equipment and 2-3% for Building Value for)
Consider depreciation = 13% of FCI
Manufacturing of Cumene
Gharda institute of technology, lavel Page 49
Depreciation = (0.136.803108) + (0.030.611210
8)
= Rs. 0.9027108
ii. Local Taxes: (1-4% of fixed capital investment)
Consider the local taxes = 3% of fixed capital investment
= 0.036.803108
= Rs. 0.2041108
iii. Insurances: (0.4-1% of fixed capital investment)
Consider the Insurance = 0.7% of fixed capital investment
= 0.0076.803108
= Rs. 0.0476108
iv. Rent: (8-12% of value of rented land and buildings)
Consider rent = 10% of value of rented land and buildings
= 10% of ((0.09168108) + (0.611210
8))
= Rs. 0.0703x108
Thus, Fixed Charges = Rs. 1.2247108
B. Direct Production Cost: (about 60% of total product cost)
Now we have Fixed charges = 10-20% of total product charges (given)
Consider the Fixed charges = 15% of total product cost
Total product charge = fixed charges/15%
= 1.2247108/15%
= 1.2247108/0.15
= Rs. 8.1647108
i. Raw Materials: (10-50% of total product cost)
Consider the cost of raw materials,
= 25% of total product cost
Manufacturing of Cumene
Gharda institute of technology, lavel Page 50
Raw material cost = 25% of 8.1647108
= 0.258.1647108
= Rs. 2.0412108
ii. Operating Labour (OL): (10-20% of total product cost)
Consider the cost of operating labour,
= 12% of total product cost
= 12% of 8.1647108
= 0.128.1647108
= Rs. 0.9797108
iii. Direct Supervisory and Clerical Labour (DS & CL): (10-25% of OL)
Consider the cost for Direct supervisory and clerical labour,
= 12% of OL
= 12% of 0.9797108
= 0.120.9797108
= Rs. 0.1176108
iv. Utilities: (10-20% of total product cost)
Consider the cost of Utilities,
= 12% of total product cost
= 12% of 8.1647108
= 0.128.1647108
= Rs. 0.9797108
v. Maintenance and repairs (M & R): (2-10% of fixed capital investment)
Consider the maintenance and repair cost,
= 5% of fixed capital investment
Manufacturing of Cumene
Gharda institute of technology, lavel Page 51
= 0.056.803108
= Rs. 0.3402108
vi. Operating Supplies: (10-20% of M & R or 0.5-1% of FCI)
Consider the cost of Operating supplies,
= 15% of M & R
= 15% of 0.3402108
= 0.15 0.3402108
= Rs. 0.05103108
vii. Laboratory Charges: (10-20% of OL)
Consider the Laboratory charges,
= 15% of OL
= 15% of 0.9797108
= 0.150.9797108
= Rs. 0.1469108
viii. Patent and Royalties: (0-6% of total product cost)
Consider the cost of Patent and royalties,
= 4% of total product cost
= 4% of 8.1647108
= 0.048.1647108
= Rs. 0.3266108
Direct Production Cost = Rs. 4.983108 ----- (61% of TPC)
C. Plant overhead Costs (50-70% of Operating labour, supervision, and maintenance or 5-15%
of total product cost); includes for the following: general plant upkeep and overhead, payroll
overhead, packaging, medical services, safety and protection, restaurants, recreation, salvage,
laboratories, and storage facilities.
Manufacturing of Cumene
Gharda institute of technology, lavel Page 52
Consider the plant overhead cost,
= 60% of OL, DS & CL, and M & R
= 60% of ((0.9797108) + (0.117610
8) + (0.340210
8))
= Rs. 0.8625108
Thus,Manufacture cost = Direct production cost + Fixed charges + Plant overhead costs.
Manufacture cost = (4.983108) + (6.80310
8) + (0.862510
8)
Manufacture cost = Rs. 12.6485108
II. General Expenses = Administrative costs + distribution and selling costs + research and
development costs
A. Administrative costs:(2-6% of total product cost)
Consider the Administrative costs ,
= 5% of total product cost
= 0.05 8.1647108
= Rs. 0.4082108
B. Distribution and Selling costs: (2-20% of total product cost); includes costs for sales
offices, salesmen, shipping, and advertising.
Consider the Distribution and selling costs,
= 15% of total product cost
= 15% of 8.1647108
= 0.15 8.1647108
= Rs. 1.2247108
C. Research and Development costs: (about 5% of total product cost)
Consider the Research and development costs,
= 5% of total product cost
= 5% of 8.1647108
Manufacturing of Cumene
Gharda institute of technology, lavel Page 53
= 0.05 8.1647108
= Rs. 0.4082108
D. Financing (interest): (0-10% of total capital investment)
Consider interest = 5% of total capital investment
= 5% of 7.8235108
= 0.057.8235108
= Rs. 0.3912108
= Rs. 2.4323108
IV. Total Product cost = Manufacture cost + General Expenses
= (12.6485108) + (2.432310
8)
= Rs. 15.0808108
V. Gross Earnings/Income:
Wholesale Selling Price of cumene per kg = Rs.53
Total Income = Selling price Quantity of product manufactured
= 53 x 30000000
= Rs. 15.9108
Gross income = Total Income Total capital investment
= (15.9108) (8.1647108)
= Rs. 7.7353108
Let the Tax rate be 45% (common)
Net Profit = Gross income - Taxes
= Gross income (1- Tax rate)
= 7.7353 x 108(1-0.45)
= Rs. 4.2544108
Manufacturing of Cumene
Gharda institute of technology, lavel Page 54
Pay back period = FCI/(net profit)
= 6.803*108/4.2544*10
8
= 1.6.
Rate of return = net profit* 100/(total capital investment)
= 4.2544*108*100
/ 7.8235*10
8
= 54.38 %
Manufacturing of Cumene
Gharda institute of technology, lavel Page 55
Chapter 12
ENVIRONMENTAL AND HAZOP STUDY
Environmental Considerations:
Vigilance is required in both the design and operation of process plant to ensure that legal
standards are met and that no harm is done to the environment. Considerations must be given to:
(1) All emissions to land, air, water.
(2) Waste management.
(3) Smells.
(4) Noise.
(5) The visual impact.
(6) Any other nuisances.
(7) The environmental friendliness of the products.
Waste Management:
Waste arises mainly as by products or unused reactants from the process, or as off- specification
product produced through mis-operation.
Gaseous Waste:
Gaseous effluents which contain toxic or noxious substances will need treatment before
discharge into the atmosphere. Gaseous pollutants can be removed by absorbtion or adsorbtion.
Finely dispersed solids can be removed by scrubbing, or using electrostatic precipitators.
Flammable gases can be burnt.
Liquid Waste:
The waste liquids from a chemical process, other than aqueous effluents will usually be
flammable and can be disposed of by burning in suitable designed incinerators. The gases
leaving an incinerator may be scrubbed, & acid gases neutralized.
Aqueous Waste:
The principal factors which determine the nature of an aqueous industrial effluent and on which
strict controls will be placed by the responsible authority are:
(1) pH.
(2) Suspended solid.
(3) Toxicity.
(4) Biological oxygen demand.
Manufacturing of Cumene
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The pH can be adjusted by the addition of acid or alkali. Lime is frequently used to neutralize
acidic effluents. Suspended solids can be removed by settling, using clarifiers. For some
effluents it will be possible to reduce the toxicity to acceptable level by dilution. Other effluents
will need chemical treatment. The oxygen concentration on water course must be maintained at a
level sufficient to support aquatic life. It is measured by a standard BOD test.
Toxicological data:
The toxicological data for a cumene plant is usually supposed to have the following values on the
various environmental parameters as given below: Threshold limit value 50 ppm, Skin effects
primary irritant, Absorption through skin slowly absorbed, Narcotic properties yes, Depressant
properties yes. Medical examination for workers required in some countries Other precautions as
for all aromatics.
Noise:
It can cause a serious nuisance in the neighbourhood of a process plant. Noisy equipment should,
as far as practicable, be sited well away from the site boundary. Earth banks and screens of trees
can be used to reduce the noise level perceived outside the site.
Visual Impact:
Large equipments such as storage tanks, can be painted to blend in with, or even contrast with,
the surroundings. Landscaping and screening by belts of trees can also help improve the overall
appearance of the site.
11.1 MATERIAL SAFETY DATA SHEET
11.1.1 HAZARDS IDENTIFICATION
Inhalation -
Breathing high concentrations may be harmful. Mist or vapor can irritate the throat and lungs.
Breathing this material may cause central nervous system depression with symptoms including
nausea, headache, dizziness, fatigue, drowsiness, or unconsciousness.
Eye Contact -
This material can cause eye irritation with tearing, redness, or a stinging or burning feeling.
Further, it can cause swelling of the eyes with blurred vision. Effects may become more serious
with repeated or prolonged contact.
Skin Contact -
Manufacturing of Cumene
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May cause mild skin irritation with redness and/or an itching or burning feeling. Effects may
become more serious with repeated or prolonged contact. It is likely that some components of
this material are able to pass into the body through the skin and may cause similar effects as from
breathing or swallowing it.
Ingestion -
Swallowing this material may be harmful. Swallowing this material may cause stomach or
intestinal upset with pain, nausea, and/or diarrhea. This material can get into the lungs during
swallowing or vomiting. Small amounts in the lungs can cause lung damage, possibly leading to
chronic lung dysfunction or death. Swallowing this material may cause effects.
Chronic Health Effects Summary -
Secondary effects of ingestion and subsequent aspiration into the lungs may cause pneumatocele
(lung cavity) formation and chronic lung dysfunction.
Conditions Aggravated by Exposure -
Disorders of the following organs or organ systems that may be aggravated by significant
exposure to this material or its components include: Skin, Respiratory System, Central Nervous
System (CNS).
Target Organs
May cause damage to the following organs: kidneys, liver, mucous membranes, spleen, upper
respiratory tract, skin, adrenal, central nervous system (CNS), eye, lens or cornea.
Carcinogenic Potential
This product is not known to contain any components at concentrations above 0.1% which are
considered carcinogenic by OSHA, IARC or NTP.
11.1.2 FIRST AID MEASURES
Take proper precautions to ensure your own health and safety before attempting rescue or
providing first aid.
Inhalation
Move victim to fresh air. If victim is not breathing, immediately begin rescue breathing. If
breathing is difficult, 100 percent humidified oxygen should be administered by a qualified
individual. Seek medical attention immediately. Keep the affected individual warm and at rest.
Manufacturing of Cumene
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Eye Contact
Check for and remove contact lenses. Flush eyes with cool, clean, low-pressure water for at least
15 minutes while occasionally lifting and lowering eyelids. Do not use eye ointment unless
directed to by a physician. Seek medical attention if excessive tearing, irritation, or pain persists.
Skin Contact
Remove contaminated shoes and clothing. Flush affected area with large amounts of water. If
skin surface is damaged, apply a clean dressing and seek medical attention. Do not use
ointments. If skin surface is not damaged, clean affected area thoroughly with mild soap and
water. Seek medical attention if tissue appears damaged or if pain or irritation persists.
Ingestion
Do not induce vomiting. If spontaneous vomiting is about to occur, place victims head below
knees. If victim is drowsy or unconscious, place on the left side with head down. Never give
anything by mouth to a person who is not fully conscious. Do not leave victim unattended. Seek
medical attention immediately.
11.1.3 FIRE FIGHTING MEASURES
NFPA Flammability Classification - NFPA Class-IC flammable liquid.
Flash Point - Closed cup: 36C (96F). (Pensky-Martens.)
Lower Flammable Limit - AP 0.9 %
Upper Flammable Limit - AP 6.5 %
Autoignition Temperature - 424C (795F)
Hazardous Combustion Products - Carbon dioxide, carbon monoxide, smoke, fumes, and/or
unburned hydrocarbons.
Special Properties
This material releases vapors at or below ambient temperatures. When mixed with air in certain
proportions and exposed to an ignition source, its vapor can cause a flash fire. Use only with
adequate ventilation. Vapors are heavier than air and may travel long distances along the ground
to an ignition source and flash back. A vapor and air mixture can create an explosion hazard in
confined spaces such as sewers. If container is not properly cooled, it can rupture in the heat of a
fire.
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Extinguishing Media
SMALL FIRE: Use dry chemicals, carbon dioxide, foam, water fog, or inert gas (nitrogen).
LARGE FIRE: Use foam, water fog, or water spray. Water fog and spray are effective in
cooling containers and adjacent structures. However, water can cause frothing and/or may not
extinguish the fire. Water can be used to cool the external walls of vessels to prevent excessive
pressure, autoignition or explosion. Do not use a solid stream of water directly on the fire as the
water may spread the fire to a larger area.
Protection of Fire fighters
Firefighters must use full bunker gear including NIOSH-approved positive pressure self-
contained breathing apparatus to protect against potential hazardous combustion or
decomposition products and oxygen deficiencies. Evacuate area and fight the fire from a
maximum distance or use unmanned hose holders or monitor nozzles. Cover pooling liquid with
foam. Containers can build pressure if exposed to radiant heat; cool adjacent containers with
flooding quantities of water until well after the fire is out. Withdraw immediately from the area
if there is a rising sound from a venting safety device or discoloration of vessels, tanks, or
pipelines. Be aware that burning liquid will float on water. Notify appropriate authorities of
potential fire and explosion hazard if liquid enter sewers or waterways.
11.1.4 ACCIDENTAL RELEASE MEASURES
Flammable Liquid! Release causes an immediate fire or explosion hazard. Evacuate all non-
essential personnel from immediate area and establish a "regulated zone" with site control and
security. A vapor-suppressing foam may be used to reduce vapors. Eliminate all ignition sources.
All equipment used when handling this material must be grounded. Stop the leak if it can done
without risk. Do not touch or walk through spilled material. Remove spillage immediately from
hard, smooth walking areas.Prevent spilled material from entering waterways, sewers,
basements, or confined areas. Absorb or cover with dry earth, sand, or other non-combustible
material and transfer to appropriate waste containers. Use clean, non-sparking tools to collect
absorbed material. For large spills, secure the area and control access. Prevent spilled material
from entering sewers, storm drains, other drainage systems, and natural waterways. Dike far
ahead of a liquid spill to ensure complete collection. Water mist or spray may be used to reduce
or disperse vapors; but, it may not prevent ignition in closed spaces. This material will float on
water and its run-off may create an explosion or fire hazard. Verify that responders are properly
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HAZWOPER-trained and wearing appropriate respiratory equipment and fire-resistant protective
clothing during cleanup operations. In an urban area, cleanup spill as soon as possible; in natural
environments, cleanup on advice from specialists. Pick up freeliquid for recycle and/or disposal
if it can be accomplished safely with explosion-proof equipment. Collect any excess material
with absorbant pads, sand, or other inert non-combustible absorbent materials. Place into
appropriate waste containers for later disposal. Comply with all applicable local, state and
federal laws and regulations.
11.1.5 HANDLING AND STORAGE
Handling
A spill or leak can cause an immediate fire or explosion hazard. Keep containers closed and do
not handle or store near heat, sparks, or any other potential ignition sources. Avoid contact with
oxidizing agents. Do not breathe vapor. Use only with adequate ventilation and personal
protection. Never siphon by mouth. Avoid contact with eyes, skin, and clothing. Prevent contact
with food and tobacco products. Do not take internally. When performing repairs and
maintenance on contaminated equipment, keep unnecessary persons away from the area.
Eliminate all potential ignition sources. Drain and purge equipment, as necessary, to remove
material residues. Follow proper entry procedures, including compliance with 29 CFR 1910.146
prior to entering confined spaces such as tanks or pits. Use gloves constructed of impervious
materials and protective clothing if direct contact is anticipated. Use appropriate respiratory
protection when concentrations exceed any established occupational exposure level Promptly
remove contaminated clothing. Wash exposed skin thoroughly with soap and water after
handling. Non-equilibrium conditions may increase the fire hazard associated with this product.
A static electrical charge can accumulate when this material is flowing through pipes, nozzles or
filters and when it is agitated. A static spark discharge can ignite accumulated vapors
particularly during dry weather conditions. Always bond receiving containers to the fill pipe
before and during loading. Always confirm that receiving container is properly grounded.
Bonding and grounding alone may be inadequate to eliminate fire and explosion hazards
associated with electrostatic charges. Carefully review operations that may increase the risks
associated with static electricity such as tank and container filling, tank cleaning, sampling,
gauging, loading, filtering, mixing, agitation, etc. In addition to bonding and grounding, efforts
to mitigate the hazards of an electrostatic discharge may include, but are not limited to,
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ventilation, inerting and/or reduction of transfer velocities. Dissipation of electrostatic charges
may be improved with the use of conductivity additives when used with other mitigation efforts,
including bonding and grounding. Always keep nozzle in contact with the container throughout
the loading process. Do not fill any portable container in or on a vehicle. Do not use compressed
air for filling, discharging or other handling operations. Product container is not designed for
elevated pressure. Do not pressurize, cut, weld, braze solder, drill, or grind on containers. Do not
expose product containers to flames, sparks, heat or other potential ignition sources. Empty
containers may contain material residues which can ignite with explosive force. Observe label
precautions.
Storage
Keep container tightly closed. Store in a cool, dry, well-ventilated area. Store only in approved
containers. Do not store with oxidizing agents. Do not store at elevated temperatures or in direct
sunlight. Protect containers against physical damage. Head spaces in tanks and other containers
may contain a mixture of air and vapor in the flammable range. Vapor may be ignited by static
discharge. Storage area must meet OSHA requirements and applicable fire codes. Additional
information regarding the design and control of hazards associated with the handling and storage
of flammable and combustible liquids may be found in professional and industrial documents
including, but not limited to, the National Fire Protection Association (NFPA) publications
NFPA 30 ("Flammable and Combustible Liquid Code"), NFPA 77 ("Recommended Practice on
Static Electricity") and the American Petroleum Institute (API) Recommended Practice 2003,
(Protection Against Ignitions Arising Out of Static, Lightning, and Stray Currents"). Consult
appropriate federal, state and local authorities before reusing, reconditioning, reclaiming,
recycling or disposing of empty containers or waste residues of this product.
11.1.6 EXPOSURE CONTROLS AND PERSONAL PROTECTION
Engineering Controls
Provide ventilation or other engineering controls to keep the airborne concentrations of vapor or
mists below the applicable workplace exposure limits indicated below. All electrical equipment
should comply with the National Electrical Code. An emergency eye wash station and safety
shower should be located near the work-station.
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Personal Protective Equipment
Personal protective equipment should be selected based upon the conditions under which this
material is used. A hazard assessment of the work area for PPE requirements should be
conducted by a qualified professional pursuant to OSHA regulations. The following pictograms
represent the minimum requirements for personal protective equipment. For certain operations,
additional PPE may be required.
Eye Protection
Safety glasses equipped with side shields are recommended as minimum protection in industrial
settings. Chemical goggles should be worn during transfer operations or when there is a
likelihood of misting, splashing, or spraying of this material. A suitable emergency eye wash
water and safety shower should be located near the work station.
Hand Protection
Avoid skin contact. Use heavy duty gloves constructed of chemical resistant materials such as
Viton or heavy nitrile rubber. Wash hands with plenty of mild soap and water before eating,
drinking, smoking, use of toilet facilities or leaving work. Do not use gasoline, kerosene,
solvents or harsh abrasives as skin cleaners.
Body Protection
Avoid skin contact. Wear long-sleeved fire-retardant garments (e.g., Nomex) while working
with flammable and combustible liquids. Additional chemical-resistant protective gear may be
required if splashing or spraying conditions exist. This may include an apron, boots and
additional facial protection. If product comes in contact with clothing, immediately remove
soaked clothing and shower. Promptly remove and discard contaminated leather goods.
Respiratory Protection
For known vapor concentrations above the occupational exposure guidelines (see below), use a
NIOSH-approved organic vapor respirator if adequate protection is provided. Protection factors
vary depending upon the type of respirator used. Respirators should be used in accordance with
OSHA requirements (29 CFR 1910.134).
General Comments
Use of this material in spaces without adequate ventilation may result in generation of hazardous
levels of combustion products and/or inadequate oxygen levels forbreathing. Odor is an
inadequate warning for hazardous conditions.
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