Developing and Integrating Sustainable Chemical

Processes into Existing Petro-Chemical Plant Complexes

Outline
IntroductiontoSustainableDevelopment
ResearchVision
Biomassconversionprocesses,AspenHYSYS2006 designs,
AspenICARUSProcessEvaluator2006 costestimations
Integrationofbiotechnologyinexistingplantcomplex
Conclusions

Sustainability
Sustainabilityreferstointegratingdevelopmentinthreeaspects
Economic
Environmental
Societal

Therearenumerousapproachestoattemptanintegrationof
theseaspectsbyworldorganizations,countriesandindustries.

CorporateSustainability

Acompanyssuccessdependsonmaximizingtheprofitasexpressedbelow.
Profit= ProductSales RawMaterialCosts EnergyCosts

TheprofitequationabovecanbeexpandedtomeettheTripleBottomline
criteriaofsustainability.
Thiswillincorporatetheeconomiccostsexpandedtoenvironmentalcostsand
societalcosts(alsoreferredtoasthesustainableorsustainabilitycosts)
TripleBottomLine= ProductSales+ SustainableCredits
RawMaterialCosts EnergyCosts
EnvironmentalCosts SustainableCosts

TripleBottomLine=Profit nvironmentalCosts+ Sustainable(Credits Costs)

ResearchVision
Proposeabiomassbasedchemicalindustryinthechemical
productioncomplexintheGulfCoastRegionandtheLower
MississippiRiverCorridor.
Utilizecarbondioxidefromallprocessesinthecomplextomake
chemicalsandproducealgaeforbiomassfeedstock.
AssigncoststotheTripleBottomlineEquationcomponents.
ProposeaMixedIntegerNonLinearProgrammingproblemto
maximizetheTripleBottomlinebasedonconstraints:multiplant
materialandenergybalances,productdemand,rawmaterial
availability,andplantcapacities
UseChemicalComplexAnalysisSystemtoobtainParetooptimal
solutionstotheMINLPproblem
UseMonteCarlosimulationstodeterminesensitivity ofoptimal
solution

Proposed Biomass-Based Complex Extension

BiomassProcesses
Thefollowingbiomassconversionprocessesare
consideredforintegrationintothechemicalcomplex
superstructure:

Fermentation
Anaerobicdigestion
Transesterification
Gasification
Directconversionofplantoils

Pretreatmentofbiomassisnecessarybeforeanyof
thebiomassconversionprocesses.

Transesterification
Glycerolderivatives
Glycerol

1,3 propanediol
Propyleneglycol

Natural
Oils

Transesterification

FAMEorFAEE

Polyurethane
polyols

Transesterificationprocessisthetreatmentofvegetableoilwithanalcohol
andacatalysttoproduceestersandglycerol.
Methanolorethanolisusedasalcoholforfattyacidmethylorethylesters
(FAME/FAEE).
Theseesterscanbetransformedtochemicals.
Glycerolisproduced~10%byweightintheprocess.
Glycerolcanbeintroducedtothepropylenechain

HYSYSDesignofTransesterification
Glycerol

Transesterification
Thermodynamic UNIQUAC
model

Transesterification

FAMEorFAEE

Thedesignisdividedintothreesections
Transesterificationreaction
Methylesterpurification
Glycerolrecoveryandpurification

10milliongallonsperyear1ofFattyAcid
MethylEster(FAME)produced
FAMEisutilizedinmanufactureofpolymers
Glycerolisusedinmanufactureof
propyleneglycol
Furtherworkincludesevaluationin
feedstockchanges,e.g.Algaeoil
1 Design

Reactants

Methanol
SoybeanOil

Catalyst

1.78%(w/w)Sodium
Methylateinmethanol

Products

MethylEster
Glycerol

Temperature

60oC

MethylEsterPurification
Washagents

Water
HCl

GlycerolRecoveryandPurification
Purification
Agents

NaOH
Water
HCl

based on Super-Pro Designer model obtained from M.J. Haas et al., Bioresource Technology 97 (2006) 671-678

HYSYSDesignofTransesterification
MaterialBalance
InletMaterialStreams MassFlow(kg/hr)
Methanol
612
Catalyst
133
Soybeanoil
4250
HCL
345
Water(wash)
166
NaOH
21

OutletMaterialStreams MassFlow(kg/hr)
FAME
4260
Glycerol
393
Water
349
Sodiumchloride
177
Methanol
223

EnergyBalance
EnergyFlow(kJ/hr)
Type
Required(kg/hr)
EnergyRequired
25x105 HPSteam47bar,260oC
1,500
Coolingwater
47,900
EnergyLiberated
40x105

ICARUSProcessEvaluatorEconomicAnalysisofTransesterification
EconomicAnalysis
EconomicLife

10

PlantCapacity

9,277,000

GALLONS/YearMethylEster
@3.000USD/GALLONS

6,795,000

USD

TotalProjectCapitalCost

Years

TotalOperatingCost

21,000,000

USD/Year

TotalRawMaterialsCost

18,000,000

USD/Year

128,000

USD/Year

28,000,000

USD/Year

TotalUtilitiesCost
TotalProductSales
DesiredRateofReturn
NetPresentValue
P.O.Period

20

Percent/Year

12,000,000

USD

4.75

Year

CashFlowandNetPresentValue
Time

10

CF(CashFlowforProject) Cost/Period($106)

0 10.41

0.58

5.65

6.14

6.66

7.21

7.79

8.42

9.09 11.49

NPV(NetPresentValue) Cost/Period($106)

0 8.68 8.27 5.00 2.04

0.64

3.05

5.23

7.19

8.95 10.81

HYSYSDesignofPropyleneGlycol
Hydrogen,200oC,200psi
Glycerol

Propyleneglycol

Thedesignisbasedonalowpressure
(200psi)andtemperature(200oC)
processforhydrogenationofglycerolto
propyleneglycol1
65,000metrictonofpropyleneglycolis
producedperyear2

1 Design
2

Hydrogenolysis
Thermodynamicmodel

UNIQUAC

Reactants

Glycerol
Hydrogen

Catalyst

CopperChromite

Products

PropyleneGlycol
Water

Temperature

200oC

Pressure

200psi

based on experimental results from Dasari, M. A. et al. 2005, Applied Catalysis, A: General, Vol. 281, p. 225-231.
Capacity based on Ashland/Cargill joint venture of process converting glycerol to propylene glycol

HYSYSDesignofPropyleneGlycol
MaterialBalance
InletMaterialStreams MassFlow(kg/hr)

OutletMaterialStreams MassFlow(kg/hr)

Glycerol

PropyleneGlycol

9,130

WaterVapor

3,150

Unreactedglycerol

9,210

Hydrogen
Catalyst
Water

20,300
242
1,060
991

EnergyBalance
EnergyFlow(kJ/hr)

Type

EnergyRequired

302x105 HPSteam47bar,260oC

EnergyLiberated

276x105

Coolingwater

Required(kg/hr)
18,200
330,000

ICARUSProcessEvaluatorEconomicAnalysisofPropyleneGlycol
EconomicAnalysis
ProjectDuration
PlantCapacity
TotalProjectCapitalCost

10
145,000,000
5,180,000

Years
LB/Yearpropylene
glycol@0.815USD/LB
USD

TotalOperatingCost

113,000,000

USD/Year

TotalRawMaterialsCost

102,000,000

USD/Year

1,540,000

USD/Year

169,000,000

USD/Year

TotalUtilitiesCost
TotalProductSales
DesiredRateofReturn
NetPresentValue
P.O.Period

20

Percent/Year

602,000,000

USD

2.38

Year

CashFlowandNetPresentValue
Time

10

CF(CashFlowforProject) Cost/Period($106)

0 16.98

NPV(NetPresentValue) Cost/Period($106)

0 14.15 9.27 15.25 37.27 57.00 74,.67 90.48 104.62 117.25 128.74

7.03 42.39 45.65 49.09 52.77 56.66 60.79 65.18 71.12

Fermentation
Sugars

Ethanolderivatives

Fermentation
Ethanol
C6
Sugars

Starches

Enzyme
Conversion

Ethylenederivatives

C5/C6Sugars

Celluloseand
Hemicellulose

Ethylene

SuccinicAcid

Succinicacidderivatives

Butanol

Butanolderivatives

AcidorEnzymeHydrolysis

Fermentationistheenzymecatalyzedtransformationofanorganiccompound.
Fermentationenzymesreactwithhexoseandpentosetoformproducts.
Enzymeselectiondeterminesproduct:
SaccharomycesCervisiae(C6),Escherichiacoli(C5&C6),Zymomonasmobilis(C6) Ethanol
EngineeredEschericiacoli,A.succiniciproducens SuccinicAcid
Engineeriedmicroorganism Butanol
LacticAcidProducingBacteria(LAB) LacticAcid

Ethanolfromfermentationcanbeconvertedtoethyleneandintroducedinto
theethylenechain.

DesignofFermentation
Sugars
Starches

Fermentation

Ethanol

Celluloseand
Hemicellulose

ThedesignisbasedonNRELs1 lignocellulosicbiomassto
ethanolprocessdesignwhichconverts2000m.t./dayofcorn
stover.
Useofdifferentfeedstockarebeingevaluated.

1 Design

based on results from Aden A. et al., NREL/TP-510-32438, National Renewable Energy Laboratory, Golden, CO, (June 2002)

HYSYSdesignofEthylene
300oC,Fluidizedbedprocess,99%conversion
Ethanol

Ethylene

Dehydrogenation

Designisbasedondehydrogenation
ofethanoltoethylene1
Thecapacityoftheplantisbasedon
a200,000m.t./yrethylene
productionfacilityproposedby
BraskeminBrazil2

1 Design
2

Thermodynamicmodel

UNIQUAC

Reactants

Ethanol

Catalyst

Activatedsilica
alumina

Products

Ethylene
Water

Temperature

300oC

based on process described by Wells, G. M., 1999, Handbook of Petrochemicals and Processes, Sec. Ed., Pg 207-208
Capacity based on Braskem proposed ethanol to ethylene plant in Brazil http://www.braskem.com.br/

HYSYSdesignofEthylene
MaterialBalance
InletMaterialStreams MassFlow(kg/hr)
Ethanol
46,000
Water(wash)
9,000

OutletMaterialStreams MassFlow(kg/hr)
Ethylene
28,000
Water
28,000

EnergyBalance
EnergyFlow(kJ/hr)
Type
Required(kg/hr)
EnergyRequired
1,139x105 HPSteam47bar,260oC
69,000
Coolingwater
778,000
EnergyLiberated
650x105

AnaerobicDigestion
Celluloseand
Hemicellulose

Anaerobic
Biodigestion

CH4

AceticAcid

Aceticacidderivatives

Anaerobicdigestionofbiomassisthetreatmentofbiomasswith amixedculture
ofbacteriainabsenceofoxygentoproducemethane(biogas)and carbondioxide.
Fourstages:hydrolysis,acidogenesis,acetogenesisandmethanogenesis
MixAlco process Inhibitsfourthstageofmethaneproductionusingiodoform
(CHI3)orbromoform(CHBr3).Reducescostofprocessbyusingmixedcultureof
bacteriafromcattlerumen.Producesmixedalcohols,carboxylicacidsand
ketones.

Anaerobic
Biodigestion

Gasification
Ammonia
Celluloseand
Hemicellulose

Ammoniaderivatives

Syngas

Gasification

Methanol

Methanolderivatives

Hydrogen

- Biomasscanbegasifiedtoproduceofsyngas
- Syngascanbeconvertedtochemicalslikemethanol,ammoniaand
hydrogen

IndustryPerspective
EthyleneandPropyleneare
basicbuildingblocksforpolymers
andchemicalintermediates

Approximately1%ofglobalenergy
marketand3%ofglobaloilandgas
marketisusedaschemical
feedstock

oftheenergyand massofthe
chemicalfeedstockisretainedin
theendproduct
3

1 CEP, March 2008, Pg S7-S14

2 http://www.braskem.com.br/site/portal_braskem/en/
sala_de_imprensa/sala_de_imprensa_detalhes_6970.aspx
3 http://www.ashland.com/press_room/news_detail.asp?s=1543

IndustriesinLouisiana
PetrochemicalcomplexinthelowerMississippiRiverCorridor

Dow
DuPont
BASF
Shell
Exxon
Monsanto
IMCAgrico
UnionCarbide

.andothers

Photo: Peterson, 2000

Base Case of Plants in the Lower Mississippi River Corridor

Biomass Based Complex

Integrated Chemical Production Complex

Chemicalslike
methylamines,
methanol,acetic
acidetc.fromCO2

CO2
Algaegrowthfor
useasbiomass

MulticriteriaOptimizationProblem
Maximize:

w1P+w2S

P=ProductSales EconomicCosts EnvironmentalCosts

S=Sustainability(Credits Costs)
w1 +w2 =1
Subjectto:
Multiplantmaterialandenergybalance
Productdemand
Rawmaterialavailability
Plantcapacities

CostsintheTriple
Bottomline

RelativePriceperunitenergyofvarious
feedstocksandproducts,quotedintheir
traditionalunitsandcalibratedto$/GJ

Contourplotofproductioncostplus
returnoninvestmentasafunctionof
capitalandvariablecosts(basedon
1000Gg/yearofolefinproduction)
CEP, March 2008, Pg S7-S14

CostsintheTriple
Bottomline

Capitalandoperatingcostsfor
150milliongallonsperyear
(MMGPY)ofgasolineequivalent
plants,2005dollars

Biofpr, 1:49-56 (2007)

CostsintheTripleBottomline

Environmentalcosts
AIChE/TCAreport1 listsenvironmentalcostsasapproximately20%oftotal
manufacturingcostandrawmaterialas30%ofmanufacturingcosts(data
providedbyAmoco,DuPontandNovartis).
Environmentalcostestimatedas67%ofrawmaterialcost.

Sustainablecosts
Sustainablecostswereestimatedfromresultsgivenforpowergenerationin
AIChE/TCAreport 1.
Alternatemethodstoestimatesustainablecostsarebeingevaluated.
Component
CarbonDioxide

1 Constable,

SustainableCost($/m.t.)
3.25

NOx

1,030

SOx

192

D. et al., Total Cost Assessment Methodology; Internal Managerial Decision Making Tool, AIChE, ISBN 0-8169-0807-9, July ,1999.

BiomassComponents

links

Hexose

links

Pentose

Complexpolymer
containing
phenolic
Triglycerides
compounds

Feedstock
Algae
ConsumesCO2 inacontinuous
processusingexhaustfrompower
plant(40%CO2 and86%NO)
Canbeseparatedintooiland
carbohydrates
Highoildensityyieldsproduction
rateof15,000gallons/acre
comparedto60gallons/acrefor
soybeans
Waterusedcanberecycledand
wastewatercanbeusedas
comparedtooilseedcrops high
waterdemand
Highgrowthrates,canbeharvested
daily

UseAlgaetoconsumeCO2 from
chemicalproductionprocesses
Algaebecomesfeedstockforthe
productionofoiland
carbohydratesforchemicals

Photo: National Geographic, October 2007

Feedstock
VerticalAlgaeReactorfed
continuouslywithatmospheric
CO2
16timesgrowingvolumein
thesameareaisachievedin
theseverticalreactorsas
opposedtoalgalponds
Closedsystemensures
optimalgrowthandreduces
harmfulexternalinfluences
Oilextractionfromalgaeis
thecostlieststepintheprocess
Photo: FUEL | 4th Quarter 2007

FeedstockinLouisiana

Corn

Sugarcane

WasteBiomassfromtheagriculture,
forestryresidues,municipalsolid
waste

Soybean

Switchgrass

http://plants.usda.gov/

TransportationtoGulfCoast

Waterways from the midwestern states can provide excellent transport for biomass
feedstock to the Gulf Coast.
Industries in the Lower Mississippi River Corridor can receive the feedstock and convert
to chemicals.
Map created from http://nationalatlas.gov/

Summary
ExtendtheChemicalProductionComplexintheLower
MississippiRiverCorridortoinclude:
Biomassbasedchemicalproductioncomplex
CO2 utilizationfromthecomplex

Obtaintherelationsfortheabovechemicalplants:
Availabilityofrawmaterials
Demandforproduct
Plantcapacities
Materialandenergybalanceequations

AssignTripleBottomlinecosts:
Economiccosts
Environmentalcosts
Sustainablecreditsandcosts

Summary

DefineMulticriteriaOptimizationProblemwithconstraints
UseMixedIntegerNonLinearProgrammingGlobalOptimizationand Local
OptimizationSolverstoobtainParetooptimalsolutionsoftheproblem
below.
- GAMS/BARON GlobalOptimizer
- GAMS/DICOPT LocalOptimizer
w1P+w2S
P=ProductSales EconomicCosts EnvironmentalCosts
S=Sustainability(Credits Costs)
w1 +w2 =1

UseMonteCarloAnalysistodeterminesensitivityoftheoptimal solution.
FollowtheproceduretoincludeplantsintheGulfCoastRegion(Texas,
Louisiana,Mississippi,Alabama)
Methodologycanbeappliedtootherchemicalcomplexesoftheworld.

Research White Paper and Presentation available at www.mpri.lsu.edu