Sustainable Processing via Process Intensification · PDF fileSustainable Processing via...

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Sustainable Processing via Process Intensification

Laurence R. WeatherleyDepartment of Chemical and Petroleum Engineering, The University of Kansas, Lawrence, KS66045, USA

[email protected]

Chemical and Petroleum Engineering

Scope of Talk• Environmental goals and sustainable processing• Historical context • The drivers for change and sustainable processing • Sustainable processing at the molecular level• Devices for sustainable processing • Enhanced process and product design for

sustainability • Conclusions


Environmental Goals?• Avoid pollution• Minimize hazard• Minimize waste of raw

materials• If possible use renewable

feedstocks (including energy)

• Maximize process efficiency• Minimize emissions and use

of energy

• Low impact products• Consistency with economic

criteria


Industrial Britain - 1840 The UK Chemical Industry in 1870

WR Duncan in The Chemical Industry eds D Sharp, TF Twist, Ellis Horwood SCI 1982

• 1800-1900 – Metals• 1870-1970 – Chemicals and Polymers

A brief snapshot of the historical development of process industry


Steam driven transport


Copyright © 2005 DuPont. All rights reserved. The DuPont Oval Logo, DuPontTM, The miracles of scienceTM and all products denoted are registered trademarks or trademarks of E. I. du Pont de Nemours and Company or its affiliates.

From gunpowder to nylon


Sustainability – some early measures

1900 – Chlorination of drinking water

1956 and 1968– Clean Air Acts (UK)

1863 – the Alkali Works Regulations Act (UK)


The emergence of the oil industry 1960’s, 1970’s


The Thirst for Oil


1960’s, 1970’s


Copyright© 2006 - INVISTA, INVISTA Building, 4123 East 37th Street North, Wichita, KS 67220 - All Rights Reserved

The Growth of Petrochemical Products - Fibers and Materials


Demand for functionality in product design became the over-riding consideration


The emergence of branding


….and people want lifestyle rewards…


Changes in the chemical industry post-1980• Great change in feedstock patterns• Movement of oil producer countries into

petrochemicals• Globalization of labor markets• Huge demand for sophisticated products with

emphasis on performance and functionality• Environmental awareness!

R. Malpas “A Geochemical view of the year 2000” in The Chemical Industry eds D Sharp, TF Twist, Ellis Horwood SCI 1982


The Chemical Industry in 2009- Energy & Transportation

Catalyst

Fuel Cell

Fuel

Courtesy of Dr John O’Connell and AICHE


Drug Design

Drug Manufacture

Engineered Fertilizers, Pesticides

Controlled Drug Delivery

The Chemical Industry in 2009 -Synthetic Pharmaceutical and Biological

Products



Zone refining of Silicon

Microprocessor manufacuring

Etching, Lithography, Chemical Vapor Deposition

Nanostuctured materials

Liquid Crystals Flat Displays

The Chemical Industry in 2009 - Materials for Communication



Environmental AwarenessIndustrial Britain - 1840 150 years on - Alaska - Exxon

Valdiz


• Environmental awareness seen in terms of:

– End of pipe solutions -Dispersion

– Compliance - Avoidance of Prosecution

– Minimum Expenditure– Operation at the legal

boundaries

• Awareness extends beyond Pollution Prevention by treatment

– Significant environmental impacts recognised

– Public concerns at climate change and resource depletion

– Rebalancing of views on economic growth

– Emergence of stronger legislative frameworks

– Emergence of business and “green” ethics

– Emergence of biotechnology

Pre-1980 1980’s and 1990’s


The Drivers for Change

• Business• Political and Legal • The emergence of the concept of

Sustainable Processing


Business

Niall Fitzgerald – Chief Executive Unilever 2003. Guardian Weekly 10th July 2003 - “Companies need to understand the power wrought by consumers and accept that being good corporate citizens is the bedrock of business success, not a bolt-on extra - If the only thing that concerned me was doubling profits I could do it, but we would be out of business a few years later. The person who employs me is the person who buys Flora Margarine or Persil: 150 million people a day buy a Unilever brand. If we are not respectful of the environment and of the societieswhere we operate, people will cease to trust us and our brands, will cease to buy them, and we are out of business”


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US Pollution Prevention Act of 1990

PollutionPrevention

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Recycling

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PP Act 1990 considered Birth of Green Chemistry and Engineering:pollution prevention vs. treatment and remediation

Adapted from Mary Kirchoff


• The Goal - Sustainable Development

• The Means – Sustainable Processing?


What is Sustainable Processing?

• Sustainable Processing is a design, construction and operational philosophy that can lead to energy, capital, environmental and safety benefits through radical reductions in plant size and improvements in efficient use of raw materials.

Sustainable Processinginvolves the development of more sustainable, safer, more efficient, more effective, and more economic processes

D O Jones HSE Report Research Contract Report 105/1996 – Sustainable Engineering of Batch Exothermic Reactors – HSE – United Kingdomhttp://www.bhrgroup.co.uk/pi/

Possible Definitions


Sustainable processing

Process Intensification

Molecular

Devices

Product and Process Design


Molecular Level Sustainable Processing

New catalystsNew solvents

Biological reactions



• Phenol Synthesis – traditional route –via cumene – two step, and co-product

Alkyl benzene cumene hydroperoxide phenol acetone

Hazardous!! Co-product



• Phenol Synthesis – intensified route – one step hydroxylation of benzene, no co-product

benzene nitrous oxide phenol

OH

N2O+ZSM-5 (MFI) type zeolite catalyst

BUT…….U.Hiemer et al Chem Eng J vol. 101, 2004, 17-22

+ N2

New catalyst



• BUT– Reaction is highly exothermic– High temperature reduces reaction

selectivity towards phenol– Nitrous oxide and benzene ….. Potential

explosive!!!

U.Hiemer et al Chem Eng J vol. 101, 2004, 17-22



• Possible Solution– Use a microreactor with

the ability to remove heat directly from the catalyst to the wall of the reactor

– Can operate under nearly isothermal conditions

– Microreactor => high space time yields and much reduced inventory => more sustainable

U.Hiemer et al Chem Eng J vol. 101, 2004, 17-22

Falling Film micro-reactor 2002Holger Löwe, Volker Hessel, and Andreas Mueller - Pure Appl. Chem., Vol. 74, No. 12, pp. 2271–2276,



• New catalysts• New solvents• Exploitation of Biological Reactions


Sustainable Processing – New Solvents

• Ionic Liquids– Salts that are liquid at

ambient temperatures.– Have stable liquid range of

over 300 K.– Very low vapor pressure at

room temperature.– Potential to replace many

volatile organic solvents – Judicious variation of the

alkane chains on the organic cation

– May generate an infinite set of designer solvents

• Ionic liquids – downside– Expensive?– Preparation usually involves use

of other solvents– Recycling also usually involves

other solvents to extract unwanted residues

– Toxic persistent (to some extent) – End of life disposal – Materials incompatibility?


anionanionOrganicOrganiccationcation

Designer solvents Designer solvents -- flexibility of choosing flexibility of choosing functional groups to make ionic liquidsfunctional groups to make ionic liquids

AlkylammoniumAlkylphosphoniumAlkylnitrideN,N’-dialkylimidazoliumN-alkylpyridinium

Halide-based (Cl-, Br-, F-)Halogeno-based (BF4

-, PF6-)

Halogenoaluminium(III)

NO3-, ClO4

-,HSO4-

SO3-, CF3SO3

-

(CF3SO2)2N-

(CF3SO2)3C-

From KN Marsh, University of Canterbury, NZ


From Chauvin’s Nobel Prize Lecture 2005. The homogeneous catalyst based on a transition metal based ionic liquid in an ionic liquid. Hydrocarbon separates in second phase

From KN Marsh, University of Canterbury, NZ and

Ionic Liquids – dimerization• Difasol – new process for the

dimerization of butenes to isooctenes using ionic liquids

• New process provides significant benefits over the existing homogeneous Dimersol X process,

• Currently in operation in five industrial plants, producing nearly 200 000 tons/year of isooctenes.

(Freemantle, M. Chem. Eng. News 1998, 76, ); (J.Dupont, R.F. de Souza, and P.A. Z. Suarez.(2002) „Ionic Liquid(Molten Salt) Phase Organometallic Catalysis“ Chem. Rev., 102, 36673692)


Molecular Level – New Solvents

• Carbon Dioxide– Low cost– Non-toxic– Properties well

understood– Straightforward product

isolation– Wide control of solvation

and selectivity behavior (via temp, pressure, and use of entrainers)

– High diffusion rates offer potential for increased reaction rates

– Potential for homogeneous catalytic processes

– Excellent medium for oxidation and reduction reactions

– Combination with conventional solvents (CXL’s) and entrainers -> further options


Carbon dioxide - CXLs

• CXLs are a continuum of compressible media generated when various amounts of dense phase CO2 are added to an organic solvent.

• Provide enhanced solubilities of transition metal complexes for performing homogeneous catalysis

• CXLs offer both reaction and environmental benefits.

• Example – hydroformlylation of 1-octene

Hong Jin, Bala Subramaniam, Anindya Ghosh and Jon Tunge (2006) AIChE Journal July 2006 Vol. 52, No. 7 2575-2581



• CO2 -down side– High pressure processing required– High capital cost at large scale– Lack of good design data

Green Solvents Fundamentals and Industrial Applications - Dr Chris Rayner, University of Leeds


Enzymatic catalysis

Sweetwater(containing glycerol)

Fatty acidFat

Steam

Process water

Flashing

Splittingtower

Colgate-Emery fat splitting process• High temperature 250C• High pressure 75 bar• High energy consumption• Dirty product => separation costs and

effluent

Biocatalysis• Lipase catalysed oil hydrolysis • Operates at near ambient temperature

and atmospheric pressure• High reaction selectivity is possible• Reduction in downstream separation

costs and waste generation



C3H8(OOCR)3 + H2O ⇔ C3H8(OH)(OOCR)2 + R-COOH triglyceride water diglyceride fatty acid C3H8(OH)(OOCR)2 + H2O ⇔ C3H8(OH)2(OOCR) + R-COOH diglyceride water monoglyceride fatty acid C3H8(OH)2(OOCR) + H2O ⇔ C3H8(OH)3 + R-COOH monoglyceride water glycerol fatty acid

Electrically Intensified Enzyme Catalysed Oil Hydrolysis


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Comparison of steam hydrolysis with enzymatic hydrolysis of sunflower oil

Electrically Intensified Enzyme Catalysed Oil Hydrolysis

A six-fold increase in specific reaction rate


Devices for Sustainable Processing

• Achievement of better multiphase contact, heat and mass transfer– Spinning disks– Static mixers– Microreactors– Electrostatic Reactors– Oscillatory Baffled

Reactors– Microchannel devices– HIGEE

• Achievement of better sourcing and use of energy– Fuel cells– Integrated energy

management models– Renewable energy

generation


www.protensive.com


• The Spinning Disk Reactor– High heat and mass

transfer coefficients– Plug flow– Intensive mixing

capability– Short residence times– Low fouling

• The ProtensiveSpinning Disk Reactor– Thin film processing –

potential for radiation induced polymerization

– Inventory reduction from 5m3 equivalent to 10mL

– Reaction requiring 30 minutes reaction time at 70C might be reduced to 7 seconds at 150C in an SDR

Spinning Disk Contactor with impinging jets –biodiesel synthesis

Canola oil

Sodium Methoxide

Spinning Disc

Stator

Fixed disk

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71.62 Average

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Conversion, wt%

Run no.

SDR - Residence time - < 5s

15 minutes



Dr Paul Stonestreethttp://www.cheng.cam.ac.uk/research/groups/polymer/OFM/pi.html

X. W.Ni and A Fitch J Chem Tech Biotech vol 78 2003

Oscillatory Baffled Flow Reactor

• Enhanced mixing at very low and uniform shear

• Linear scale-up• Large volume reduction• Large footprint reduction• Large increases in energy

efficiency


What levels of Sustainable Processing are there?

– Molecular– Device– Product and Process Design


Business drivers• More products and faster• Higher yield• Lower cost• Process stability and

reliability• Short pay-back time

Political drivers• Consent limits• Incentives for renewables• Carbon tax and trading

The responses• Process integration – energy

based optimization• Multi-purpose processing• Integration / elimination of

process steps• Holistic design strategy• Development of new chemical

technologies (e.g. for renewable feedstocks)

• Development of new separation techniques (e.g.sequestration)

• Product miniaturization• Process intensification

Sustainable Product and Process Design

Temporal and spatial changes in landscape carbon dynamics with fuel crop choicesInteractions with multiple climate scenarios

Regulatory ComplianceAtmospheric LoadingsFuel ComparisonsFuel StorageEngine Settings

DDriveabilityriveabilityEEmissionsmissionsPPerformanceerformanceEEfficiencyfficiencyCCostost

Ankistrodesmus –model algae strain for reactor experiments

BIOFUELSFeedstock to Tailpipe©

Initiative

Fuel ProductionFuel Production(Chemical and Environmental Engineering)

Feedstock ProductionFeedstock Production(Ecology and Evolutionary Biology/Environmental and Chemical Engineering)

Ecosystem Level ProcessesEcosystem Level Processes(Ecology and Evolutionary Biology/Geography)

Fuel AnalysisFuel Analysis(Mechanical and Environmental Engineering)

CO2 emissions influencing climate

Feedstock to Fuel PropertiesCreate Designer FuelsProcess IntensificationASTM Standard Compliance

Feedstock ViabilityReactor Design and ConstructionExtraction and Separation


Sustainable Processing “Needs” driven or “Innovation” driven?

Realistic process improvement and optimization?

Scientists, inventors and technologists finding an application for interesting, chemistry, or a device or a concept? ?

political?

We must solve this problem or improve our process if the business is to survive?

Needs driven Innovation driven


Sustainable Processing• Needs … created by

– hostile environments– high flux environments– complex environments– unstable environments– better reliability needed– better economics needed– space is at a premium (offshore, vehicle energy, portable

power…..) – visible impact reduction– alternative feedstocks– effluent reduction– cost of services– geography of the business– ………….


Conclusions• Businesses and other organizations are more

accountable for environmental impacts than ever before

• Stakeholders are increasingly well-informed and expect higher and higher standards of performance in order to meet wider environmental and social objectives.

• Major business benefits can accrue through the application of sustainable processing

• PI Innovations at the molecular level, at the device level and in process & product design are crucial components in sustainable engineering

www.icheme.org/sustainability

* Keith Guy - The Competitive Edge The Competitive Edge -- The Integration of PI into the Business ProcessThe Integration of PI into the Business Process “Balancing Risk and Reward”The Royal Institution of Great Britain, London: 19th November 2003

Thank you

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