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May 2007 Escape 17 1
Renewable Raw Materials: Challenge and Chance for CAPE
Alexandre C. Dimian
UNIVERSITY OF AMSTERDAM - NLFACULTY OF SCIENCE van ‘t Hoff Institute for Molecular Sciences (HIMS)
May 2007 Escape -17 2
The future is not what it used to be !
I don't try to describe the future. I try to prevent it.
Ray Bradbury (b. 1920)
May 2007 Escape -17 3
Outline
1. Learning from history2. Biorefinery concept3. Green Chemistry & Green Engineering4. Old & New Thermodynamics5. Challenges for Conceptual Process Design6. Process Simulation issues7. Applications8. Conclusions
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Chemical product tree
The survival of Chemical Process Industries implies massive use of Renewable Raw Materials (RRM)
Gani, 2004
May 2007 Escape -17 5
Back to first oil crisis, Dec. 1973
Synfuels and alternative olefin feedstock
Emergence of process simulationCorporate packages: Shell, Total, DSM, ICI, Specialised providers: SimSci, AspenTech, …
May 1983: CAPE meeting in ParisFirst main-frame flowsheeting packages(Process, Aspen-Plus,… )
May 2007 Escape -17 6
Progress as outcome from crisis
Comprehensive simulation of phase equilibrium separation processes
Generalised Thermodynamics methodsEquations of state & Liquid activity methods ( 50+)Databases for pure components and mixtures
M & H balance of complex plants with recyclesComprehensive algorithms for complex units handling various mixtures (non-ideal + supercritical)
Distillation inside-out, Gibbs free energy minimisationFlowsheeting: Topological analysis, Equation solving Data reconciliation
Efficient use of Materials and EnergyHierarchical approach in Process DesignOptimisation (SQP, MINLP, …)Pinch Analysis
May 2007 Escape -17 7
Un-sustainability of today’s CPI
Inefficient materials valorisation & recycling90% of materials end-up as waste
High energy consumption based on finite resources
Oil, coal, natural gas
Negative impact on humans and biospherewaste, emissions, hazards and toxics
May 2007 Escape -17 8
Tomorrow ?
Peak of petroleum in 2030-50 ?Cost of oil barrel over 100 USD ? Switch on coal for “Carbon appetite”?Globalisation and new needs in emerging countries Climate change and treats on the environmentConcentration of fossil resources
C2 & C3 135
BTX 50
Terephtalic acid 12
Adipic acid 1.5
Methanol 25
Acetone 3.2
Sucrose 140
D-glucose 30
Ethanol 25
Sugar acids 1.7
Amino acids 2.2
Biomass180 bill. tons/yr
Carbohydrates 75%
Lignin 20%
Fats, Proteins, Terpenoids,
Alkaloids, Nucleic Acids 5%
May 2007 Escape -17 11
Targets for Renewable Raw Materials (RRM)
EU 2001 2005 2010 2030
Energy 7.5% 12.5% 26%
Fuels 1.4% 2.8 % 5.75% 20%Chemicals 8-10% ?
USA 2002 2005 2010 2030Energy 2.8% 4% 5%Fuels 0.5% 4% 10% 20%
Chemicals 5% 12% 18% 25%
May 2007 Escape -17 13
Oil & Gas
Fuels & Energy
Petro-Chemistry
Biomass
Fuels & Energy-Bio-ethanol-Bio-diesel-Bio-gas
Bio-chemistryBasic & Fine chemicalsBiopolymers
Refinery Biorefinery
May 2007 Escape -17 16
Bio-refinery concept (1)
FeedstocksFood & feed grainsLignocelluloses Municipal Solid Waste
TechnologiesBio-technologyThermo-chemicalChemical
ProductsFuelsChemicalsPolymersFine chemicals, …Energy
Phase I: fixed capabilitiesdry-milling ethanol plant from grains
Phase II: mono input / multi-product
Wet-milling of grains to starch, corn syrup, gluten, ethanol
Phase III: multi feedstock, multi-products
Bio-mass feedstockChemicals, intermediates, polymers, energy
B. Kamm, P. Gruber, M. Kamm, Biorefineries, Wiley-VCH 2005
May 2007 Escape -17 17
Bio-refinery concept (2)
Thermo-chemical platform
Pre-processing Heat & Power
Primaryproducts
FuelsChemicalsMaterials
Bio-gas platform
Sugarplatform
Carbon-rich chainsplatform
BIOMASS
Ligno -cellulosic
GlucosicLypidicMSW
Plant-products platform
May 2007 Escape -17 18
Alternative fuels
Name Origin Use Eco-efficiency
Natural gas for vehicles NGV Natural methane Fuel A
Liquefied petroleum gas LPG Oil & gas processing Fuel B
SynfuelsGas to liquidCoal to liquidBiomass to liquid
GTLCTLBTL
Rich methane gasCoal liquefactionSyngas
Gasoline or diesel substitutes
C
Ethanol BE Sugar cane, corn,… Gasoline blend B
Bio-diesel BD Oils and fats Diesel blend BHydrogen CH4, Hc, H2O Fuel cell CMethanol Syngas Fuel cell B
May 2007 Escape -17 19
Typical bio-refineries (Phase III)
LCF (lignocellulose feed)
Whole-crop
Green bio-refinery
Precursors Platforms Building blocks ChemicalsProducts
CarbohydratesStarchCelluloseHemicellulose
Lignin
Oils/Fats
Proteins
Syngas
Sugar
Lipids
Proteins
C1
C2
C3
C4
C5
C6+
Ar
Lignin
Polymers
Methanol
EthanolAcetic ac.
Lactic ac.Glycerol
Succinic ac.Fumaric ac.
FurfuralLevulinic ac.
LysineSorbitolFatty acids
Gallic ac.
HydrocarbonFormaldehyde,DimethyletherMethylamines,…
OlefinesOxo-alcohols,…
OlefinesAlcohols1,2,PDOEthersAcidsEstersAcrylates,…
Furfural, THF,
Green solvents
Polymers•PLA•Polyacylates•Polymaides•Polyurethanes•Polycarbonates•Resines
Polysaccharides
Chemicals from RRM
May 2007 Escape -17 25
Principles of Green Chemistry
1. Prevent waste formation
2. Atom efficiency
3. Les hazardous chemical syntheses
4. Efficacy of functions while reducing toxicity
5. Limited use of solvents and auxiliary materials
6. Minimise energy requirements
7. Favour the use of renewable raw materials
8. Reduce derivation
9. Use catalytic reagents
10. Favour bio-degradable products
11. Develop analytical methods for waste monitoring
12. Minimize the occurrence of hazards
Anastas et al, 1998
May 2007 Escape -17 26
Examples of Green Chemistry
TAML activator IBUFREN synthesis
Bio-catalysis synthesis of adipic acid Glycerol ethers
May 2007 Escape -17 27
Industrial Success Stories
Process RRM Chemistry Properties/Process
PLA [-O-CH(CH3)-CO-]n
CornStarch
1,3-PDOCH2(OH)-CH2-CH2(OH)
CornGlycerol
Bio-cat PTT instead PET monomers
PHA/PHBCH3-CH(OH)-CH2-COOH
Corn Bacterial synthesis
Bio-degradableBio-process or GM plant (?)
B2 Vitamin Soya Metabolic Engng
8-step synthesis in just one
Bio-degradableMedical care, food packaging-56% GHG vs PET-1.7kgCO2kg-1in LCF bioref.
Bio-cat
May 2007 Escape -17 29
An “old-fashioned” view(Prausnitz 1999)
Our time is characterised by perfecting the means while confusing the goals (A. Einstein)
Why do we need so complicated models, software, …?
What Thermodynamics can do for CPI based on RRM and bio-technology ?
Chemical Engineering Thermodynamics should be application-oriented . One area for new applications is phase equilibria for unconventional mixtures found in emerging chemical industries
May 2007 Escape -17 30
Unconventional separations
Separation method Characteristic property
Process design parameter
Chromatography•Ion exchange•Size exclusion•Hydrophobic interaction•Reversed phase •Affinity
CrystallizationL-L extraction Membranes
Charge Molecular sizePartial specific volumeHydrophobicitySVCSolubility
Partition coefficientSedimentation coefficientPermeability
L. v. d Wielen et al (TU Delft)
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Analogy of thermodynamic conceptsPrausnitz 1995-2000
Prausnitz, J. M. J. Chem. Thermo, 2003
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Wide range of applications
Medical technology
Healing of cataract disease, Prausnitz (2003)
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Quantum mechanics: a new tool for engineering thermodynamics
Phase behaviour of pure componentsSecond Virial Coefficient (SVC)
Improve group contribution methodsUNIFAC: proximity parameters Θ=a+be2+cd2
Compute ab-initio Gibbs Free energyLiquid activity coefficient
S. Sandler, Fluid Ph. Eq., 2002
May 2007 Escape -17 34
Ab-initio prediction of phase equilibrium
HF-MeOHWater-/ 1.4 dioxane
A. Klamt , COSMO-RS
May 2007 Escape -17 35
Solubility of complex molecules C. Chen, 2006NRTL-SAC (segment activity contribution)
Hydrophobic, xPolar attractive, y-Polar repulsive, y+Hydrophilic z
Analogy with COSMO but based on exp. DataPredictive value on basis of molecule-specific parameters
May 2007 Escape -17 37
12 principles of Green Engineering
1. Inherent rather than Circumstantial
2. Prevention instead of Treatment
3. Design for Separation4. Maximize Efficiency5. Output-Pulled versus
Input-Pushed 6. Conserve Complexity
7. Durability rather than Immortality
8. Meet Need, Minimize Excess
9. Minimize Material Diversity
10.Integrate Material and Energy Flows
11.Design for Commercial "Afterlife“
12.Renewable rather than Depleting
May 2007 Escape -17 39
Bio- vs petrochemical plants
Batch - Semi-batch - Continuous │ ContinuousSmall/medium scale │ Large scaleFixed -Mobile │ Fixed unitsLiquid / Solid phase │ Gas / Liquid phaseModerate P, T │ High P, T Non-conventional L-S separations │Conventional L-V separation (distillation)Intensive M & H transfer (mech. mixing) │Gradient driven mixing
May 2007 Escape -17 40
Conceptual Process Design Bio- vs petrochemical
Rate (kinetics) based │Equilibrium-stage Frequent non-linearities│ Limited non-linearities
dynamic modelling │steady-state modellingAdvanced control │ Feedback control Process Analysis, on-line Quality Control │ Data monitoring, off-line quality control
► Bio- process engineering: more high-tech
May 2007 Escape -17 41
Systematic Process Design
Methodology Bio- Petrochemical
Hierarchical Approach
+(+) +++
Combinatorialanalysis
+++ +
Pinch Analysis ++ +++
Thermo analysis ? ++
May 2007 Escape -17 42
Process Simulation tools
Methodology Bio- Petro-
Flow-sheeting (M & H balance)
Dynamics & Control
Sizing + ++User modelling + ++Operation/Scheduling ++ ++On-line optimisation (CIM) ? ++
++++(+)++++(+)
Environmentally Conscious Process DesignD. Allen, D. Shonnard, E. Pistikopoulos, U. Diwekar, R. Gani, …
ChemistryProcess Synthesis•R-Sep-Recycles•Equip. selection
Process Simulation
Process Diagnostic Summary
Alternatives
SizingProfitabilityEnvironment
Scaled gradient analysis
Multi-objectiveoptimisation
Base-case
Short-list
Detailed design
May 2007 Escape -17 45
Advanced process synthesis
Agricultural silage tofibres, LA, AA, bio-gas
Halasz, Povoden, Narodoslavsky . (2005)Friedler et al. (1992)
BIODIESEL PROCESS
Aspen-PlusTM & SuperPro Designer®
Storage 1/3 InvestmentRM 88% Manufacturing costs
R-1 S-1 S-4
S-2
S-3 D-1
C-1
T-1
R-2Waste Water
BiodieselGlycerol 85%
Methanol
Oil
Free fatty acids
Methanol recycle
Glycerol 50%Mineral acidMineral acid
Water
Crude ester
Ester
MEOH/water
MEOH/waterCatalyst
R-1
S-2
R-5
C-2
R-4
Water
NH2-C10-COOH
Glycerol
Methanol
Castor Oil
MeOH recycle
C18-ester
Heptanal
Waste
MeOH/water
NaOH
R-2
C-5C-3 C-4
S-1C-1
NH3
Heavies
H2S04
R-3
HBrH2SO4
C11-ester
C11-acidNa2SO4
Water
RILSAN polymer (Nylon 11)
Complete water recycling (reaction +process)No gas emissions, no liquid waste, only incinerated solidsPlant Simulation Model for revamping and operation
May 2007 Escape -17 48
Conclusions
Green Chemistry & Catalysis: key factors for Sustainable Processes based on RRMExpansion of Chemical Engineering Thermodynamics to bio-applicationsImbedding Computational Chemistry & Chemical Engineering ThermodynamicsMethodological approach of bio-chemical engineeringNeed of a new generation of “integrated simulators” (bio+petro) Interfacing software through CAPE-OPEN
May 2007 Escape -17 49
A bright future for Sustainable Process Industries !
Exiting research subjects
More funding from Bio-fuels
Opportunities for R&D jobs
More students……
Hence Challenge and Chance for CAPE