Catalysis for the Biorefinery.pdf

8/14/2019 Catalysis for the Biorefinery.pdf

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These slides were presented at the NSF Catalysis for Biorenewables

Conversion Workshop, held in Arlington, Virginia on April 13 and 14,

2004. These slides may not be altered or reproduced for

distribution. Any use of these slides must include an acknowledgment

of the author, their affiliation, and the National Science Foundation.


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Cameron, Cargill NSF Catalysis for Biorenewables Conversion Workshop

Catalysis for the Biorefinery

Douglas C. Cameron

NSF Workshop onCatalysis for

Biorenewables

Conversion

April 13, 2004


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Overview of Cargill

Founded in 1865 Private ownership

>95,000 employees

~65 countries

88 business units

>1,000 locations ~$60 billion in sales



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Agricultural

Value chainfood

feed Biobased

matls



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HydrocarbonTypical synthetic process

oil, gas

naphtha, gas

ethylene, propylene,

butadiene

acrylic, acetic,

maleic, propionic,

propylene oxide,

butanol

CarbohydrateTypical bioprocess

corn/ biomass

starch/ cellulose

Glucose/

other sugars

citric, itaconic, lactic

(PLA), Isosorbide, 3HP

Vegetable OilsTypical process

soybean

oil

fatty acids

soy polyols,

polymerintermediates

Industrial Products



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Cargill Biorefinery, Eddyville, Iowa



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Cargill Biorefinery, Blair, Nebraska



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Cargill Dow (CD) polymer plant, Blair, NE



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Drivers for the Bio-Industrial Revolution

Better products for consumers

More economical for industryand consumers

More dependable, renewableand lower-cost feedstocks

More environmentally friendlyproducts/processes; smallerenvironmental footprint



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Enabling the Bio-Industrial Revolution

Feedstock prices will continue to drop in realterms- Improvements in agronomic practices

- Biomass conversion technologies

Processing technology must evolve- Government must invest in basic research

- Industry must commit to invest and develop process technologyrelated to aqueous processing of dilute solutions

- New catalysts, both biological and chemical, are required

- Novel combinations of catalytic steps is needed

Product development is critical- Platform chemical concept

- Partnerships between traditional chemical and agricultural firms willneed to emerge



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Renewable Feedstocks will become

competitive with petrochemical feedstocks

0

10

20

30

40

50

60

70

80

73 75 77 79 81 83 85 87 89 91 93 95 97 99 01 03

0

5

10

15

20

25

30

35

40

Glucose Price (cents/pound)

Oil Price

($/barrel)

Crude Soybean Oil

(cents/pound)

Soyb

ean

oil,glu

cose

(cents/pound)

Oil($/barrel)



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Impact of Processing Improvements

Today Future

Processing

Gra

in

Fermentation

Feedstocks

?

Relative Cost



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Current Cargill BiorefineryIndustrial

ProductsProcessing Refining Intermediates

Citric acid

Itaconic

LysineLactic acid

Ethanol

*3-HP

*Isosorbide

Oil

Lubricants

CoatingsPolyols

Plasticizers

Thermoplastics

Urethanes

Specialtypolyesters

Monomers

Plastic

intermediates

Feedstocks:

Corn

SoyWheat

Palm

Canola Oil

Sugar

SunflowerFlax Oil

Biomass

Carbohydrate

Modified

Starches

Glucose

Protein,

Fiber

Food &

Feed

FermentationFeedstocks

Fatty acids

Glycerol

* Intermediates under development



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Vegetable oil-based examples

Current business

(Industrial Oils and Lubricants)

Emerging applications

Soybean Oil



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Industrial Oils and Lubricants

Base oils and esters

Formulated Hydraulic Fluids

Agri-SperseTM

Water Dispersable Lubricants

OxicureTM Coatings

BioTrans Transformer Dielectric Oils



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Emerging Applications of Vegetable oils

VegetableOil

Urethanepolyols

Fatty acids(biodiesel)

Glycerol

Olefins

9-decenoicAcid (9DA)



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Billions of Pounds (MDI, TDI, Polyether Polyol)

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0

4.0

`62 `64 `66 `68 `70 `72 `74 `76 `78 `80 `82 `84 `86 `88 `90 `92 `94`54 `56 `58 `60 `96`98 `00 02

4.5

5.0

Flexible foams

CASE

Rigidfoams

US Polyurethane MarketCameron, Cargill NSF Catalysis for Biorenewables Conversion Workshop


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Urethane Polyols

2.5 billion pounds per year of urethanepolyols are sold in the US each year

capacity expansion for propylene oxide-basedpolyether polyols require huge capital investments

and raw material prices are under constantupward pressure.

Cargill Industrial Bioproducts is developingoil-based alternative to PO-based polyols withimproved performance at cost parity or better



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Metathesis chemistry applied to vegetable oils

Rubber, latex,polymersdienes


Unsaturatedfatty acids

H2C=CH2

LLDPE,synthetic

lubricants

-olefins

9-decenoic(9DA)

Severalapplications


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Advances driven by new catalyst technology

RuCl

Cl

PR3

PR3Ru

Cl

Cl

PR3

NN

N

CHC(CH3)2Ph

MoCH3(CF3)2CO

CH3(CF3)2CO

CH(CH3)2

(CH3)2CH

Schrock catalyst Grubbs catalyst 2nd GenerationGrubbs catalyst



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Metathesis Catalyst Platform ConceptMetathesis Catalyst Platform Concept

9 - Decenoic

Amino Decanoic(Nylon 10)

Decanol

(Solvents, Plasticizers, Surfactants)

C-18 Diacid(Polymers)

Epoxy Resins

(Coatings)

Sebacic

(Nylon 6, 10)

Capric

(Surfactant, Synthetic Lube)

10, 11-Dioctyleicosane

(Lubricant)


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Carbohydrate-based examples

Glucaric acid

3-hydroxypropionic acid (3-HP)



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OH

OH

OH

O

HO

OH

HO

HO

OH

OH

OH

OH

(OH)2OPO

(OH)2OPO

OPO(OH)2

OPO(OH)2

OPO(OH)2

OPO(OH)2

COOH

OH

OH

OH

O

OH

HOOC

COOH

OH

HO

OH

OH

Enzyme catalysis?

Chemical catalysis?


Phytic acid

glucose

inositol

Glucaric acid

Glucuronic acid

Phytase

or

Acid catalysis

fermentation

Chemical

or

Enzyme

Oxidation

Myo-inositol

oxygenase


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PLA

CH3-CH-COOH|

OH

GlucoseEsters

Propyleneglycol

100%theoretical yield

anaerobic2-hydroxypropionicacid (lactic acid)

3-hydroxypropionic

acid

CH2-CH2-COOH|

OH

Glucose?

?

?



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3-HP

Glucose

Pyruvate

Lactate

Malonyl-CoA

Glycerol

-alanine

Metabolic pathway design

Design criteria: Energetics Maximum theoretical yield Availability of enzymes / genes Co-factor requirements of enzymes Intellectual property/FTO

Cameron, Cargill NSF Catalysis for Biorenewables Conversion WorkshopWO 02/424128


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Directed evolution from known enzyme with similarfunction

Lysine 2,3-aminomutase

Lysine 5,6-aminomutase

Find natural aminomutase Anaerobic enrichment on -alanine as sole carbon source

Approaches to getting alanine 2,3-

aminomutase


Structural relationship between lysine and


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Structural relationship between lysine and

alanineNH2

H2NO

OH

NH2

O

OH

-lysine-alanine

Lysine 2,3-

aminomutase

Alanine 2,3-

aminomutase

O

OHNH2

O

OHNH2

-alanineH2N -lysine



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Microbial catalysis/fermentation

Chemicalcatalysis

Derivativesof 3HP

Glucose 3HP


Application of 3-HP: High Solubility of 3HP Ca++ salt


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pp g y

0.1 0.4 1.1 1.2 7

3550

100

0

20

40

60

80

100

120

citrate

malate

citrate-m

alate

glycolate

lactate

acetate

propionate

3H

P

gramsof

salt/100mlwater

>


O O


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OH

O

OH

n

O

O OHO OH

1,3-propanediol

EEPhydrogenation


CH2 OH

O

CH2NH2

O

3-hydroxypropionic acid

poly(hydroxypropionate)HO OH

O

oxidation

dehydrationHO OH

OOacrylamide

malonic acid

acrylic acid

Corn or other


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Corn or other

biomass

Chemical andenzymatic

Glucose

Fermentation (metabolic engineering)

3-HP


Poly 3-HP

microbial

Acid andpowdered

copperMn-promoted

copper

Malonic acidPd and Pt

Acrylic acid 1,3-propanediol


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syncretic

\Syn*cret"ic\, a. Uniting and blending

together different systems, as of

philosophy, morals, or religion.

The biorefinery requires the blending together of different systemsof chemistry and catalysisheterogeneous, homogeneous,

enzymatic, microbial:

Syncretic chemistry??

Summary and future


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Summary and future

considerations The biorefinery is already a reality

Carbohydrate and vegetable oil prices are likely to decreaserelative to petroleum prices

The chemical industry will increasingly use renewable rawmaterials such as vegetable oils and carbohydrates

Thoughtful combination of chemical, enzymatic and microbialcatalysis (syncretic chemistry?) is essential to realize the fullpotential of the biorefinery


Acknowledgments


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AcknowledgmentsCargill BioTDC

Cargill Process Solutions TDC

Cargill Scientific Resources

Codexis

Pacific Northwest National Labs (PNNL)

Cargill Industrial Bioproducts

U.S. Department of Energy (DOE)


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