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Sustainable Processing via Process Intensification
Laurence R. WeatherleyDepartment of Chemical and Petroleum Engineering, The University of Kansas, Lawrence, KS66045, USA
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
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
Steam driven transport
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
Sustainability – some early measures
1900 – Chlorination of drinking water
1956 and 1968– Clean Air Acts (UK)
1863 – the Alkali Works Regulations Act (UK)
Chemical and Petroleum Engineering
The emergence of the oil industry 1960’s, 1970’s
Chemical and Petroleum Engineering
The Thirst for Oil
Chemical and Petroleum Engineering
1960’s, 1970’s
Chemical and Petroleum Engineering
Copyright© 2006 - INVISTA, INVISTA Building, 4123 East 37th Street North, Wichita, KS 67220 - All Rights Reserved
The Growth of Petrochemical Products - Fibers and Materials
Chemical and Petroleum Engineering
Demand for functionality in product design became the over-riding consideration
Chemical and Petroleum Engineering
The emergence of branding
Chemical and Petroleum Engineering
….and people want lifestyle rewards…
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
The Chemical Industry in 2009- Energy & Transportation
Catalyst
Fuel Cell
Fuel
Courtesy of Dr John O’Connell and AICHE
Chemical and Petroleum Engineering
Drug Design
Drug Manufacture
Engineered Fertilizers, Pesticides
Controlled Drug Delivery
The Chemical Industry in 2009 -Synthetic Pharmaceutical and Biological
Products
Courtesy of Dr John O’Connell and AICHE
Chemical and Petroleum Engineering
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
Courtesy of Dr John O’Connell and AICHE
Chemical and Petroleum Engineering
Environmental AwarenessIndustrial Britain - 1840 150 years on - Alaska - Exxon
Valdiz
Chemical and Petroleum Engineering
• 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
Chemical and Petroleum Engineering
The Drivers for Change
• Business• Political and Legal • The emergence of the concept of
Sustainable Processing
Chemical and Petroleum Engineering
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”
Chemical and Petroleum Engineering
AMFAARPAA
AJAASBCAA
ESAA-AECAFFRAA
FEAPRAIRA
NWPAACODRA/NMSPAA
FCRPAMMPAA
120
110
100
90
80
70
60
50
40
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20
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01870 1880 1890 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000
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NEPAEQIACAAEPAEEAOSHAFAWRAANPAA
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COWLDAFWLCA
MPRSAACAAACWA
SMCRASWRCASDWAA
Num
ber o
f Law
sPolitical and Legal
Chemical and Petroleum Engineering
US Pollution Prevention Act of 1990
PollutionPrevention
SourceReduction
Recycling
Treatment
Disposal
PP Act 1990 considered Birth of Green Chemistry and Engineering:pollution prevention vs. treatment and remediation
Adapted from Mary Kirchoff
Chemical and Petroleum Engineering
• The Goal - Sustainable Development
• The Means – Sustainable Processing?
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
Sustainable processing
Process Intensification
Molecular
Devices
Product and Process Design
Chemical and Petroleum Engineering
Molecular Level Sustainable Processing
New catalystsNew solvents
Biological reactions
Chemical and Petroleum Engineering
Molecular Level Sustainable Processing
• Phenol Synthesis – traditional route –via cumene – two step, and co-product
Alkyl benzene cumene hydroperoxide phenol acetone
Hazardous!! Co-product
Chemical and Petroleum Engineering
Molecular Level Sustainable Processing
• 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
Chemical and Petroleum Engineering
Molecular Level Sustainable Processing
• 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
Chemical and Petroleum Engineering
Molecular Level Sustainable Processing
• 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,
Chemical and Petroleum Engineering
Molecular Level Sustainable Processing
• New catalysts• New solvents• Exploitation of Biological Reactions
Chemical and Petroleum Engineering
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?
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
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)
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
Molecular Level Sustainable Processing
• 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
Chemical and Petroleum Engineering
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
Molecular Level Sustainable Processing
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
0
5
10
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40
0 20 40 60 80
substrate concentration %
rate
of r
eact
ion
g h-
1 m
-2
-15 KV 225 microns+15 KV 290 micronsStirred 50 microns
Specific rate of reaction vs substrate concentration
Time (min)
0 30 60 90 120 150 180 210 240 270 300
Hydro
lysis (%
)0
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Time (min)
0 30 60 90 120 150 180 210 240 270 300
Hydro
lysis (%
)0
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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
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
www.protensive.com
Devices for Sustainable Processing
• 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
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
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90.00
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0 20 40 60 80 100
time, min
Con
vers
ion,
%
Batch stirred reactor
71.62 Average
72.44 2
70.81 1
Conversion, wt%
Run no.
SDR - Residence time - < 5s
15 minutes
Chemical and Petroleum Engineering
Devices for Sustainable Processing
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
Chemical and Petroleum Engineering
What levels of Sustainable Processing are there?
– Molecular– Device– Product and Process Design
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
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
Chemical and Petroleum Engineering
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– ………….
Chemical and Petroleum Engineering
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