Oleochemicals in the Biorefinery: Glycerol and Co-Products from

Biodiesel Production

2008 Transition to a BioeconomyIntegration of Agricultural and Energy Systems

Westin Atlanta AirportAtlanta, GA

February 12 - 13, 2008

Joseph J. BozellUniversity of Tennessee

Biomass Chemistry LaboratoryForest Products CenterKnoxville, TN 37996

Overview

• The oleochemical operating unit - a component of the biorefinery

• Biodiesel - what are the challenges and the possible impact?

• Glycerol - what do we do with it?

The Oleochemical Operating Unit

Oilcrops

Soy, sunflowercastor, tallow,canola, algae…

Triglycerides

OCO

OCO

OCO

Biodiesel

Fatty acids

Glycerol HO OHOH

“oils and fats”“plant oils”

2007: 450-500 x106 gal biodiesel produced (NBB)1998: 101x106 tonnes of fats and oils produced worldwide14x106 tonnes used by chemical industry; remainder for

food uses (Pure Appl. Chem.; 2000, 72, 1255)

+ plant residue: meal and protein

COOCH3

COOH

1,6445,128Total

495495Trap Greases

5252Other Greases

167412Yellow Grease

258487Inedible Tallow

170240Edible Tallow

21137Lard

0171Tall Oils

18131Cottonseed

029Peanut

011Safflower

65113Sunflower

087Canola

115331Corn

2832,432Soy

Supply for Biodiesel MM gal/y

2001

Total US Production MM gal/yr

2001

Feedstock

Feedstock Supply Potential for Biodiesel

Source: Tyson, Shaine K., August 2002. Draft Report “Feedstocks for Biodiesel Production”, Submitted to OBP; Original data source: USDA, October 2001, Oil Crops Situation and Outlook Yearbook; USDA, Agricultural Statistics, 2001; U.S. Census Aug 8, 2001; Render, April 2002.

•Total available ~ 10% of U. S. diesel demand. (recent report: soy oil ~ 6% of diesel demand; Proc. Nat. Acad. Sci. 2006, 103, 11206)

•Competition with food impacts supply

•An impact can be made. Is it a significant impact?

Biodiesel Production Costs

• Largest cost component is feedstock (7.7 lb oil/gal biodiesel)

• Coproduct credits have room to contribute

• Needed coproduct value for competitive fuel is challenging$0.000

$0.500

$1.000

$1.500

$2.000

$2.500

$/ga

llon

biod

iese

l

High costsoy

biodiesel

Low costsoy

biodiesel

Soybiodieselcoproduct

credit

High costyel. greasebiodiesel

Low costyel. greasebiodiesel

YGbiodieselcoproduct

credit

Feedstock ReagentsLabor UtilitiesMaint, ins, tax, pkg, ship, admin InterestDepreciation CoproductNew Value Added Needed=$0.90

Source: K. S. Tyson, NREL

Coproducts Drive Cost Reduction

0.00

0.50

1.00

1.50

2.00

2.50

Bio

die

sel C

ost

($

/g

al)

Soy biodiesel andcrude glycerin

Add refined glycerol Add FAMEcoproducts

Add FA coproducts Add glycerolcoproducts

Impact of Coproducts on Biodiesel Cost

The Glycerol Potential

• Current market: 650 - 700x103 tonnes/yr• Glycerol is moving from the position of

“additive” to that of starting material (platform)

• Capture of 5% of diesel market will lead to availability of 1x106 tonnes additional glycerol

• Glycerol can serve as a model for sugar technology development

• But: Glycerol may be the limiting factor for the oleochemical operating unit

Glycerol Product Family Possibilities

HO OHOH

ROOC

HO OH

HOCHO COOH

HOOC COOH

OH

HO COOH

HOCOOH

O

HO OHOR

triglycerides

glycerol

biodiesel, fatty acids and esters

Sorona (DuPont)

PLA analogs

PLA analogs

new polyesters, nylons

representative glycerol derivative familyfermentation

fermentation

TEMPO

catalyticoxidation

catalyticoxidation

highly branchedpolymers

highly branchedpolymers

diesters

selectiveesterification

OO

O

OH

OHO

glycidol

glycerol carbonate

coatingspolymers

gas separationsolvents

cosmeticspersonal care

detergents

polyglycidolnew hyperbranched systems

dendrimers

glycerol carbonateethers and esters

existing markets

partialsaponification

catalysisalcohols

gasoline,compatibilizer

esterification

gasificationFischer-Tropschchemicals

fuel oxygenate

gasoline fuel blend

OAcAcOOAc

CO/H2

fuel applications

HOOH

selectivereduction

propylene glycolcommodity chemicals

CHOdehydration

acroleinchemical intermediate

CH2ClO epichlorohydrin

commodity chemicals

chlorinationfuel oxygenate O-tButBu-O

O-tBu

etherification

Glycerol Fuel Applications

HO OHOH

glycerol conversionand FT synthesis

gaseousalkanes

liquidhydrocarbons

naphtha, dieselkerosene

aqueous oxygenatedhydrocarbons

distillation Chemicals

Fuels

hydrogen

reforming

H2/CO light alcoholsand polyols

selective dehydrationor hydrogenation

aqueousphase reforming

upgrading

combustion Power

triglycerides

biodiesel

+

• Fischer-Tropsch synfuels• Gas turbines• Hydrogen for fuel cells• Transportation fuels

Glycerol Reduction Processes

HO OHOH

OHCOH

OH

OHOH

OHC

OH

OHC

O

HOOC

OH

OHHO

OHCOH

+ CH2O

+ CH3OH CH4

H2, Ru, Pt H2, Ru

base

base H2, Ru, Pt

base

H2, Ru, PtH2, Ru, Pt

propyleneglycol

lacticacid

ethyleneglycol

HO

Oacetol

-H2O

H2

retro-aldol

benzilic acidrearrangement

• Antifreeze• Biobased and conventional plastics• De-icers• Paints and coatings

Glycerol Oxidation Processes

HO OH

OH

HOCOOH

OH

HOOC COOH

OH

HOOC COOH

O

HO OH

OHO

COOH

O

tartronic acid mesoxalic acidglyceric acid

dihydroxyacetone hydroxypyruvic acid

PdpH=11

Pt/BipH=1.5

Pt/BipH=11

Pt/BipH=3-4

PtpH=6

Pt/BipH=1.5

• New chemical intermediates and structures

• Specialty chemicals

Glycerol Dehydration Processes

acetaldehyde formaldehyde

HO OHOH

HO OH HOCHO

CHO

HOOH

HOO

CH3CHO + CH2O

-H2O2o hydroxyl

-H2O1o hydroxyl

hydroxypropionaldehydeacrolein

hydroxyacetoneCOOR

acrylic acid and esters

• High volume chemical intermediates• Plastics, polymers• Coatings• Adsorbents

Biochemical Conversions of Glycerol

COOH

OOH

HOHO OH

OH

HO OHOH

glucose

glycerol

acrylic acidCOOH

OH

lactic acid

COOH

CHO

HO

HO

3-hydroxypropionic acid

3-hydroxypropionaldehyde

byproducts

Clostridiumpropionicum

Lactobacillusreuteri

hypothetical

modifiedE. coli

-H2O

HO OH CHO

acrolein1,3-PDODuPont Sorona

[O]

• High volume commodities• New polymers, textiles

Economic Considerations

1.00 (+ 61%)0.80 (+29%)0.611.05dPropylene glycola

0.92 (+70%)0.72 (+33%)0.540.97Epichlorohydrina

1.12 (+53%)0.92 (+26%)0.731.17Acrolein/acrylic acida

- 650.250.72Purified glycerolc

- 800.050.24Crude glycerineb

+ 1000.440.22Propylenea

Δ crude glycerol (% difference

from propylene)

Δ purified glycerol (% difference

from propylene)

Δ propylene% change,

2003 -2007

Cost /lb (current)

Cost/lb (2003)

a) Chemical Economics Handbook;b) DOE Top 10 Report on Chemicals from Biomass;

c) Curr. Opin. Biotech. 2007, 18, 213, oleochemical industry representatives;d) list price for industrial grade propylene glycol; USP grade is 0.71/lb

Economic Considerations

1.00 (+ 61%)0.80 (+29%)0.611.05dPropylene glycola

0.92 (+70%)0.72 (+33%)0.540.97Epichlorohydrina

1.12 (+53%)0.92 (+26%)0.731.17Acrolein/acrylic acida

- 650.250.72Purified glycerolc

- 800.050.24Crude glycerineb

+ 1000.440.22Propylenea

Δ crude glycerol (% difference

from propylene)

Δ purified glycerol (% difference

from propylene)

Δ propylene% change,

2003 -2007

Cost /lb (current)

Cost/lb (2003)

a) Chemical Economics Handbook;b) DOE Top 10 Report on Chemicals from Biomass;

c) Curr. Opin. Biotech. 2007, 18, 213, oleochemical industry representatives;d) list price for industrial grade propylene glycol; USP grade is 0.71/lb

Economic Considerations

1.00 (+ 61%)0.80 (+29%)0.611.05dPropylene glycola

0.92 (+70%)0.72 (+33%)0.540.97Epichlorohydrina

1.12 (+53%)0.92 (+26%)0.731.17Acrolein/acrylic acida

- 650.250.72Purified glycerolc

- 800.050.24Crude glycerineb

+ 1000.440.22Propylenea

Δ crude glycerol (% difference

from propylene)

Δ purified glycerol (% difference

from propylene)

Δ propylene% change,

2003 -2007

Cost /lb (current)

Cost/lb (2003)

a) Chemical Economics Handbook;b) DOE Top 10 Report on Chemicals from Biomass;

c) Curr. Opin. Biotech. 2007, 18, 213, oleochemical industry representatives;d) list price for industrial grade propylene glycol; USP grade is 0.71/lb

Derivative Production Potential

0.78 x 1094.1 x 109Epichlorohydrin

2.6 x 109 (acrylic acid)2.5 x 109 (acrolein)3.2 x 109 (acrylic

acid)

Acrolein/acrylic acid

1.17 x 1093.4 x 109Propylene glycol

288 x 106 (2004)4.1 x 109Glycerola

Current market (lb)Potential available (lb)Chemical

a) Available glycerol calculated assuming a biodiesel industry producing 5 x 109 gal/yr

Summary

• Oleochemicals are a key component of the integrated biorefinery concept

• Oleochemicals could be the best initial bridge between the biorefinery and the petrochemical refinery

• Integrating biodiesel production with production of chemicals provides an economically attractive process approach

• New uses for glycerol will help drive greater biodiesel production

An Integrated Oleochemical Operating Unit

Oil CropsRenderingProducts

Com

mon

con

vers

ion

and

sepa

ratio

n st

eps

Fatty Acids

Glycerol

Biodiesel

Chemicals/Products

Chemical/Products

Protein MealChemicals/Products

Animal Feed

OilFuel, Refinery Feed

Chemical/Products

Research Interest in Biodiesel and Glycerol is Booming

25

2 36

35

3

7

2022

38

68

0

10

20

30

40

50

60

70

Nu

mb

er

of

cita

tio

ns

1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007Year

Number of WOS citations - (glycerin* OR glycerol*) AND biodies*

$1.00/galtax credit

1331

1330

40 46 51 56

100115

196

312

494

0

100

200

300

400

500

Nu

mb

er

of

cita

tio

ns

1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007Year

Number of WOS citations: biodies*

Glycerol citations

Biodiesel citations

Cold Flow Limits Use of Fats and Greases

-100

102030

4050

6070

0% 5% 10% 20% 35% 50% 100%

CFPP

o F

Soy Canola Lard Ed. Tallow ined. Tallow YG #1 YG #2

Oil Prices and Yield

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

0 10 20 30 40 50 60 70 80

Yield of oil (%)

soy cornsunflower

castor

linseed peanut

tung

safflower

cottonseed

Source: Chemical Economics Handbook"Fats and Oils Industry Overview"

inedibletallow

Market Scenarios

0

500

1000

1500

2000

2500

Soy Soy + YG S+YG+AF S+YG+AF+TG All sources w/ coproducts

Mil

gal/y

r

0

0.5

1

1.5

2

2.5

3

$/ga

l B10

0

Volume High Cost Low CostSource: K. S. Tyson, NREL

Consumption of New Glycerol Supplies

• Existing markets?–New glycerol from “small” biodiesel

effort in Europe consumed by existing market

–No blockbuster markets for glycerol; typical for exhibited price point

–Growing competition from SE Asia: est. 200x103 tonnes of capacity

Consumption of New Glycerol Supplies

• Recovery of previous markets, capture of new market segments– Example: alkyd resins, market size 1691

x106 lb in 2000Polyol USD / ton

Glycerol 1200 - 1600Trimethylol propane 1,278Pentaerythritol 1,278Propylene glycol 1,000Ethylene glycol 667Sorbitol (70 %) 400

Source: Claude, S. Fett/Lipid 1999, 101, 101

US Consumption of Diesel, 1998-2006

Source:http://www.eia.doe.gov/oil_gas/petroleum/info_glance/distillate.html

0

10000

20000

30000

40000

50000

60000

70000

Mil

lio

n g

all

on

s

US Total

on-highway

residential

comm

ercial

industrial

oil company

farm

electric power

railroad

maritim

e

Sector

US distillate consumption 1998-2006

1998 1999 2000 2001 2002 2003 2004 2005 2006