renewable raw materials: challenge and chance …escape17.upb.ro/edocs/doc/key_lecture escape...

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)


Outline

1. Learning from history2. Biorefinery concept3. Green Chemistry & Green Engineering4. Old & New Thermodynamics5. Challenges for Conceptual Process Design6. Process Simulation issues7. Applications8. Conclusions


Chemical product tree

The survival of Chemical Process Industries implies massive use of Renewable Raw Materials (RRM)

Gani, 2004


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,… )


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


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


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


Bio-industry vs Petro-industry

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%


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%


Biorefinery concept


Oil & Gas

Fuels & Energy

Petro-Chemistry

Biomass

Fuels & Energy-Bio-ethanol-Bio-diesel-Bio-gas

Bio-chemistryBasic & Fine chemicalsBiopolymers

Refinery Biorefinery


Bio-refinery definition (Natural Renewable Energy Laboratory )


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


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


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


Typical bio-refineries (Phase III)

LCF (lignocellulose feed)

Whole-crop

Green bio-refinery


LCF bio-refinery


Whole-crop bio-refinery


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


Green Chemistry


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


Examples of Green Chemistry

TAML activator IBUFREN synthesis

Bio-catalysis synthesis of adipic acid Glycerol ethers


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


Thermodynamic issues


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


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)


Analogy of thermodynamic conceptsPrausnitz 1995-2000

Prausnitz, J. M. J. Chem. Thermo, 2003


Wide range of applications

Medical technology

Healing of cataract disease, Prausnitz (2003)


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


Ab-initio prediction of phase equilibrium

HF-MeOHWater-/ 1.4 dioxane

A. Klamt , COSMO-RS


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


PROCESS DESIGN


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


BASF eco-efficiency measure


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


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


Systematic Process Design

Methodology Bio- Petrochemical

Hierarchical Approach

+(+) +++

Combinatorialanalysis

+++ +

Pinch Analysis ++ +++

Thermo analysis ? ++


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


Some applications


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


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


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


Man's yesterday may ne'er be like his morrow; Nought may endure but Mutability.

Percy Bysshe Shelley (1792-1822), British poet.

The Change only lasts forever

renewable raw materials: challenge and chance …escape17.upb.ro/edocs/doc/key_lecture escape...

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