Industrial Chemicals from Industrial Chemicals from BiorenewablesBiorenewables

Brent ShanksBrent Shanks

Chemical & Biological Engineering DepartmentChemical & Biological Engineering Department

Iowa State UniversityIowa State University

OutlineOutline

BackgroundBackground

Industrial chemicalsIndustrial chemicals– Overview of the current industry Overview of the current industry – Role of biorenewablesRole of biorenewables

Let’s start with some perspectiveLet’s start with some perspective

Transportation fuel demand (2003)Transportation fuel demand (2003)– Gasoline: 8,900,000 barrels/dayGasoline: 8,900,000 barrels/day– Diesel: 3,900,000 barrels/dayDiesel: 3,900,000 barrels/day

Biorenewable fuelsBiorenewable fuels– Ethanol: 440,000 barrels/day (2005)Ethanol: 440,000 barrels/day (2005)– Biodiesel: ~1000 barrels/day (2005)Biodiesel: ~1000 barrels/day (2005)

Maximum U.S. Production CapacityMaximum U.S. Production Capacity

CornCorn– Production: 11 billion bushels/yearProduction: 11 billion bushels/year– Biofuel Potential: 2,000,000 barrels/dayBiofuel Potential: 2,000,000 barrels/day

SoybeansSoybeans– Production: 3 billion bushels/yearProduction: 3 billion bushels/year– Biofuel Potential: 260,000 barrels/dayBiofuel Potential: 260,000 barrels/day

RoughRough U.S. Biofuel Economics U.S. Biofuel Economics

EthanolEthanol BiodieselBiodiesel

Feedstock, cpgFeedstock, cpg 180180 400400

Opex & Capex, cpgOpex & Capex, cpg 7575 4040

TotalTotal 255255 440440

Equivalent Crude Equivalent Crude Price, $/barrelPrice, $/barrel

9696 167167

Lignocellulosic BiomassLignocellulosic BiomassLignocellulosic BiomassLignocellulosic Biomass

Cellulose: 38%–50%

Most abundant form of carbon in biosphere

Polymer of glucose

Hemicellulose: 23%–32%

Polymer of 5- and 6-carbon sugars

Xylose is the second most abundant sugar in the biosphere

Lignin: 15%–25%

Complex aromatic structure

p-hydroxyphenylpropene building blocks

Personal Care Products Building Materials

$400+ billion Enterprise

U.S. Chemical EnterpriseU.S. Chemical Enterprise

Chemical IndustryChemical Industry

SustainabilitySustainability

One use Carbon Renewable Carbon

Why Biorenewable Industrial Chemicals?Why Biorenewable Industrial Chemicals?

Better match between demand and feedstock.Better match between demand and feedstock.

Selling price higher for chemicals than fuels.Selling price higher for chemicals than fuels.

Table 1: 50 Largest Volume Organic Chemicals Demanda

kg x 106/yr Growthb

%/yr Pricec $/kg

Derived Form

1 ethylene 24,000 2.5 0.33-0.75 2 propylene 13,500 4.3 0.29-0.51 3 ethylene

dichloride 11,800 4 0.31-0.42 ethylene

4 methanol 9,100 3-4 0.09-0.53 synthesis gas 5 methyl tert-

butyl ether 7,900 0.5 1.01-2.07 isobutene/methanol

6 vinyl chloride 7,100 3 0.31-0.62 ethylene 7 benzene 7,000 2 0.22-0.68 8 ethylbenzene 6,800 4 0.35-1.10 ethylene/benzene 9 styrene 5,500 3 0.46-1.19 ethylene/benzene 10 ethanol 5,400 4 0.46-1.01 11 terephthalic acid 4,500 4-5 0.49-0.90 p-xylene 12 formaldehyde 4,500 3 0.18-0.77 methanol 13 ethylene oxide 3,900 3 0.77-1.43 ethylene 14 p-xylene 3,700 3 0.37-0.88 15 cumene 3,100 3 0.33-0.68 benzene/propylene 16 ethylene glycol 3,000 3 0.44-1.46 ethylene 17 butadiene 2,450 2 0.29-0.53 18 phenol 2,060 3 0.62-1.28 benzene/propylene 19 acetic acid 1,900 3 0.51-0.88 methanol 20 acrylonitrile 1,620 2 0.86-1.17 propylene 21 -olefins 1,450 4-5 0.84-1.54 ethylene 22 propylene oxide 1,450 2-3 0.77-1.41 propylene 23 vinyl acetate 1,410 3 0.79-0.99 ethylene 24 cyclohexane 1,300 2 0.29-0.66 benzene 25 acetone 1,260 3 0.46-0.88 benzene/propylene 26 acrylic acid 953 5 1.41-1.92 propylene 27 adipic acid 925 1.5-2 1.10-1.54 benzene 28 nitrobenzene 907 5 1.46-1.65

Table 2: Large Volume Organic Polymers

Demanda

kg x 106/yr Growthb

%/yr Pricec $/kg

Derived Form

1 polyvinyl chloride

7120 4 0.46-1.04 vinyl chloride

2 polypropylene 6120 7 0.50-0.96 propylene 3 polyethylene-HD 5900 3-5 0.56-1.08 ethylene 4 polyethylene-

LLD 3860 5-7 0.84-0.88 ethylene

5 polyethylene-LD 3490 (-1)-1 0.44-1.10 ethylene 6 polystyrene 2870 2.5 0.80-1.06 styrene 7 polyethylene

terephthalate 1850 10 0.88-1.65 terephthalic acid/ethylene glycol

8 SB rubber 993 4 0.77-1.48 styrene/butadiene 9 ABS resins 771 3 1.63-3.28 acrylonitrile/butadiene/ styrene 10 polybutadiene 572 2 1.54-1.94 butadiene 11 polycarbonate 500 6-8 2.89-5.51 bisphenol-A/phosgene 12 polybutenes 386 1 0.55-1.10 butene 13 EP rubber 308 3 2.98-3.64 ethylene/propylene a U.S. demand for 1999. b Projected U.S. demand growth through 2003. c Historical low and high prices from about 1990-1999.

Birth of Industrial ChemicalsBirth of Industrial Chemicals

What do we do with this refinery byproduct?What do we do with this refinery byproduct?

Not the reasons:Not the reasons:– High value products from crude oil.High value products from crude oil.

– Production of materials with special properties.Production of materials with special properties.

Refinery ProductsRefinery Products

Components in a Barrel of Crude OilComponents in a Barrel of Crude Oil

ProductProduct gallons/barrelgallons/barrel

Chemical feedstockChemical feedstock 1.21.2

Refinery gasRefinery gas 1.91.9

PetrolPetrol 19.519.5

KeroseneKerosene 4.14.1

Diesel fuelDiesel fuel 9.29.2

LubricantsLubricants 0.50.5

Fuel oilFuel oil 4.14.1

Asphalt (bitumen)Asphalt (bitumen) 1.31.3

Ethylene and DerivativesEthylene and Derivatives

Propylene and DerivativesPropylene and Derivatives

Challenges to Replacing PetrochemicalsChallenges to Replacing Petrochemicals

Direct replacementDirect replacement– Competing with mature technology Competing with mature technology – High oxygen content in biorenewable feedstocksHigh oxygen content in biorenewable feedstocks– Dilute process streams with biorenewablesDilute process streams with biorenewables– Different trace impuritiesDifferent trace impurities

Functional replacementFunctional replacement– Competing with entrenched chemicals (polymers)Competing with entrenched chemicals (polymers)– Expense associated with introducing new large-scale Expense associated with introducing new large-scale

polymers (estimated to be about $1 billion)polymers (estimated to be about $1 billion)

Why is Oxygen Content an Issue?Why is Oxygen Content an Issue?

Ethylene from glucose:Ethylene from glucose:

fermentation to ethanol – theoretical yield 51.1%fermentation to ethanol – theoretical yield 51.1%

dehydration to ethylene – theoretical yield 60.9%dehydration to ethylene – theoretical yield 60.9%

best possible overall yield = 0.511(60.9) = 31.1% best possible overall yield = 0.511(60.9) = 31.1%

glucose at $0.15/kg glucose at $0.15/kg ethylene at $0.48/kg ethylene at $0.48/kg

just for the raw material!!!!just for the raw material!!!!

Interpolymer CompetitionInterpolymer Competition

0.18

0.2

0.22

0.24

0.26

0.28

0.3

0.32

0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22

Cost

ln (

Dem

and)

Commercial Biorenewable Industrial Commercial Biorenewable Industrial ChemicalsChemicals

GlycerolGlycerol

__________________________________________________________________________________________________

Lactic acid (polylactic acid)Lactic acid (polylactic acid)

Alkyl estersAlkyl esters

Surfactants (palm oil replacing petrochemical based)Surfactants (palm oil replacing petrochemical based)

1,3-propanediol1,3-propanediol

Biorenewable ChemicalsBiorenewable Chemicals

HO2CCO2H

HO2CCO2H

HO2CCO2H

OH

Succinic Acid

Fumaric Acid

Malic Acid

C4Diacids

OHO2C CO2H

2,5-Furandicarboxylic Acid

HOCO2H

3-Hydroxypropionic Acid

NH2

HO2CCO2H

Aspartic Acid

NH2

HO2C

Glutamic Acid

CO2H

HO2CCO2H

OH

OH

OH

OH

Glucaric Acid

HO2CCO2H

Itaconic Acid

HO2C CH3

O

Levulinic Acid

O

O

HO

3-Hydroxy-butyrolactone

HO OH

OH

Glycerol

OH

OH

OH

OH

Sorbitol

HOOHHO OH

OH

OH

OH

Xylitol

C3

C5

C4

C6

Top Value Added Chemicals from Biomass, U.S. DOE, 2004

Platform Chemical ConceptPlatform Chemical Concept

Top Value Added Chemicals from Biomass, U.S. DOE, 2004