REFINERY OF THE FUTURE: FEEDSTOCK, PROCESSES, PRODUCTS ... · REFINERY OF THE FUTURE: FEEDSTOCK, PROCESSES, PRODUCTS Jean-Luc DUBOIS EuroBioRef Summer School Lecce, September 18th

ConfidentialA European Project supported within the Seventh Framework Programme for Research and Technological Development

REFINERY OF THE FUTURE: FEEDSTOCK, PROCESSES, PRODUCTSJean-Luc DUBOISEuroBioRef Summer School

Lecce, September 18th 2011Speaker : DUBOIS Jean-Luc (ARKEMA)

The research leading to this publication has received funding from the European Union Seventh Framework Programme (FP7/20007-2013) under the grant agreement n°241718 EuroBioRef

Jean-Luc DUBOIS - EuroBioRef Summer School - Septembe r 2011 No copies without author’s prior approval

Raw materials prices

Crude Oil (Petroleum) vs Biobased raw materials


Crude Oil Price/SupplyPolitical Impact

Variation of Crude Oil Prices

2004

2000

1979

197319701965

1986

1990

1994

0

20

40

60

80

100

120

30000 40000 50000 60000 70000 80000 90000

Total world production (1000 barrels/day)

Cru

de o

il P

rices

($20

09)

Exxon Valdez ErikaAmoco CadizTorrey Canyon PrestigeKuweit Deepwater

Crude oil production costs less than 20$/bl in middle east, and most of it less than 60 $/bl


Food vs fuel

June 2010

Dec 2010Feb 2011


Evolution of Petroleum reserves

5

0

20

40

60

80

100

120

1975 1980 1985 1990 1995 2000 2005 2010 2015

Year

Num

ber

of y

ears

of c

onsu

mpt

ion

base

d on

pro

ven

rese

rves

Total WorldOECDNon-OECDEuropean UnionFormer Soviet Union

Data computed from the BP Statistical review of World Energy June 2011, www.bp.com/statisticalreview


Peak Oil

0.0

500.0

1000.0

1500.0

2000.0

2500.0

3000.0

3500.0

4000.0

4500.0

1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 2015

Year

Oil

Pro

duct

ion

(1 0

00 0

00 to

ns)

Total World

OECD

Non-OECD

OPEC

Non-OPEC**

European Union***

Former Soviet Union

Data computed from the BP Statistical review of World Energy June 2011, www.bp.com/statisticalreview

No copies without author’s prior approval

Various types of Biorefineries


Attempts of Biorefineries classificationsSource: « Towards a common classification approach for biorefinery systems », F Cherubini et al., Biofuels, Bioprod. Bioref. (2009). Classification developed within the International Energy Agency, Bioenergy Task 42.


Examples of Biorefinery schemesSource: « Towards a common classification approach for biorefinery systems », F Cherubini et al., Biofuels, Bioprod. Bioref. (2009). Classification developed within the International Energy Agency, Bioenergy Task 42.


Integrated BiorefineriesSource: « Towards a common classification approach for biorefinery systems », F Cherubini et al., Biofuels, Bioprod. Bioref. (2009). Classification developed within the International Energy Agency, Bioenergy Task 42.


Arkema’s Castor BiorefineryMarseille Saint-Menet, France

Amonolysis

BrominationCracking

Methanolysis

Crystallization

Hydrolysis


Castor


FlowsheetAminoundecanoic acid production


Elevance Renewable Sciences Metathesis-based biorefinery

● Construction in 2011 in Indonesia (association with Wilmar), Start-up Q1 or Q2 2012

● Capacity: 180 000 tons (mostly palm oil)

● 1st Step: ethenolysis of Palm Oil

● Target: high value products (olefins, C18 diester, methyldecenoate (estimate of 40 kt/y, fuels…)


Fatty acid profilesSource: « Lexicon of Lipid Nutrition », Pure Appl. Chem., Vol 73, N°4, PP 685-744, 2001 and Oleon datashee ts + internal data

0% 20% 40% 60% 80% 100%

DH12C

Crambe

Coconut

Palm Kernel

Babassu

CASTOR

Tallow

Palm

Olive

Lard

Honesty

Saff lower (high oleic)

Rapeseed HIGH erucic

Lesquerella fendleri

Groundnut

Rapeseed low erucic

Camelina

Canola

Jatropha

Corn

Cotton seed

Soya bean

Walnut

Sunflower

Linseed

Safflower (high linoleic)

Content (wt %)

SaturatedMonounsaturated

Polyunsaturated


Cargill’s BiorefinerySource: Adian Higson, NNFCC, Feb 2011


Les Sohettes – Pomacle sugars-based biorefinery


Existing BiorefineriesSource: V. Steinmetz, Biorefinery Eurovew, « Cartographie des bioraffineries en Europe », Reims, 12 Novembre 2009

● 34 existing (or projects) Biorefinery● Most of them in western Europe● None in Eastern Europe (project of a

starch biorefinery in Poland)


US Biorefineries http://www1.eere.energy.gov/biomass/integrated_biorefineries.html

No copies without author’s prior approval

Fermentation and bio-based products


Products obtained by fermentationsSource: Fermentations, by Paul BADUEL, Techniques de l’ingénieur, doc J 6004. (data of 1998-2000) � data of 1998-2000« Bioprecessing for Value-added Products from renewable resources, New technologies and applications, Ed Shang-Tian Yang, Elsevied 2007 �data of 2006Weiße Biotechnologie: Chancen für Deutschland , Stand: November 2004, Positionspapier der DECHEMA � data of 2004« Overview Biochemical process Industry » J. Krijgsman, 1 Nov 2010. � data of 2010

0.4

8

8.4

0.81.80/2.25

1.50.5

2.01.2

10.06.02020

3008 - 5200

Market Value(2004)(€/kg)

49000 @ 0.4 €

80 @ 8 €B12 15 t/yr@20000 €

20 @ 8 €

250 @ 2 €

50 @ 1.5 €

350 @ 2 €1000 @1.5 €

10 @ 10 €

Bulk: 35 kt@ 12.5 €/kg

Market Value(2010)

(kt/y @ €/kg)

>61000@ 0.6 €

1.5 / 2.0

0.6-0.7 (contract)

MarketValue(2011)

26 000

100

1200400

8001000

60

Prod. 2006(kt/y)

>18 500

8080+

40

1000290

4100190

7001500

10301.21

45#40

Prod2004(kt/y)

Drinks, Perfumes, Pharma, BiofuelsEthanol

60<5

Vitamine COthers

Vitamines (C, B2, B12)

30Xanthan GumPolysaccharides

<10Starch Industry, Glucose Industry, soaps, detergents

Enzymes (Amylase, Glucose isomerase, Protease…)

1000750

5025

Food, preservative, Chelating agentFood, preservative, Chemical synthesis, PolymerResins, Synthetic fiberPharma, Food, Paint stripper, CementFood, Industrial

Organic acidsCitric

LacticItaconic

GluconicAcetic

1000600350

1851

Animal foodFood additive, PharmaAspartame synthesisAnimal food

Nutrition

AminoacidsLysine

Glutamic /GlutamatePhenylalanine

ThreonineTryptophane

Arginine

2030-40

PenicillinOthers

Antibiotics

Prod1998-2000

ApplicationProduct


Carbon Value for many chemicals

0

2 000

4 000

6 000

8 000

10 000

12 000

14 000

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2

O/C ratio

Car

bon

Val

ue €

/ton

C

Carbon Value (August 2006)

Carbon Value - Contract Basis May 2011

Carbon Value - Spot price Basis May2011


Energy content: Fuel Versus Chemicals…Most chemical are made from Petroleum a cheap energy source

0

50

100

150

200

250

300

350

400

450

500

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2

O/C Ratio

Pro

duct

Ene

rgy

(LH

V) V

alue

Eur

o/G

J

August 2006, Energy ValueMay 2011, Contract Basis, Energy Value

May 2011, Spot Basis, Energy Value

Most of the products are a most expensive energy th an Petroleum (12 €/GJ)


Analysis of Value ChainsCurrent Market prices (April-May 2011) for Chemicals

Market Value vs Composition

0

2

4

6

8

10

0 5 10 15 20

Number of Carbons in molecule

Num

ber o

f Oxy

gen

in M

olec

ule

Contract market price 2011 €/tSpot Market price 2011 €/t

O/C=1

O/C=0.5

O/C=0.25Size of circle: Market valueas of April-May 2011

Equivalent size forGasolineJet-fuel/diesel


Profitability of an Ethanol Plant, USA

0

0.2

0.4

0.6

0.8

1

1.2

1.4

2005 2006 2007 2008 2009 2010

Year

Ret

urn

over

Var

iabl

e C

ost a

nd T

otal

Cos

t (U

S $

/gal

lon)

0.00

20.00

40.00

60.00

80.00

100.00

120.00

140.00

Pet

role

um P

rices

(U

S $

of t

he d

ay/b

arre

l)

Return over Variable CostReturn over all costsPetroleum

Data computed from Industrial Biotechnology, April 2011, Vol 7, N°2, P127


Biobased materials Market prices� issue is more on business side than on technology

Historical data for sugar and paper pulp

0

200

400

600

800

1000

1200

1/1/90

1/1/92

1/1/94

1/1/96

1/1/98

1/1/00

1/1/02

1/1/04

1/1/06

1/1/08

1/1/10

1/1/12

1/1/14

Time scale

Mar

ket v

alue

(US $

/t)

Sugar Contract 11

Imported Paper Pulp NSBK


CAPEX: Capital needed



Ethanol Projects

0

50

100

150

200

250

300

350

0 50 100 150 200 250 300 350 400

Plant Capacity (kt/yr)

CA

PE

X (

M€

, rel

oca

lized

in F

ranc

e, M

ay 2

011

)

1G Ehanol2G EthanolSyngas Fermentation Ethanol


Oil and Oil Seeds projects

0

100

200

300

400

500

600

700

0 100 200 300 400 500 600 700 800 900

Plant Capacity (kt/year)

CA

PE

X (

M€,

rel

ocal

ized

in F

ranc

e, M

ay 2

011)

Biodiesel Plants, Biodiesel Capacity

Seed Crushing and Biodiesel, Oil CapacitySeed Crushing Units, Oil capacity

Renewable Diesel, fuel Capacity


Impact of Capital Cost on Market Value

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

1.1

1.2

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

Average Product Market price (€/kg) - as of April- May 2011

Impa

ct o

f CA

PE

X o

n p

rodu

ct p

rodu

ctio

n co

st (€

/kg

)

PHA (F)

1,3-PDO (F)

Methionine (F,C)Syngas ->Ethanol (T,F)

2G EtOH

1G EtOH

Succinic (F)

EtOH�Propylene (?)

Glycerol� Epichlorohydrine (C )Lactic Acid(F)

Isobutene (F)


Drivers for Biorefineries

Sustainable development

Environmental benefit

Creating Jobs in rural environment (remote locations)Multiplication factor to include indirect jobs

Economics

CHOOSE YOUR BIOREFINERY

Fuel-Driven Chemicals/Materials-DrivenLow Value product High Value product

Low cost of processing Expensive ProcessingPre-treatment &

Minimal fractionation Fractionation requested


BioRefinery Technology Strategy OptionsWhere are you? What do you bring in and take back?

Chemicals / Fuel

Cost / Performance / Environment / Social

Technology / Feedstock / Manufacturing / Marketing

Own Plant / Operator / Joint Venture / License (technology)


Biorefinery Value Chains

● An integrated Biorefinery means:

● Creation of a new value chain

● Partnering with upstream and downstream players

● Generate sufficient revenue for farmers to secure the supply


Green Chemistry = Safe?Data from « Chapter 4: Toxins » (A Review of the Scientific Literature as it Pertains to Gulf War Illnesses, Volume 5: Chemical and Biological Warfare Agents, By: William Augerson, Ed: Rand.)

Nicotiana tobacco plantsNicotineHydrogen Cyanide, Mustard gas, Arsine, Parathion

104 to 105

The honey bee, Apis MelliferaBee VenomChlorine, White Arsenic105 to 106

Stryhnos nuxvomica bark or seed.Strychnine

Calabar bean, the seeds of Physostigma venenosum

PhysostigmineArmin (O-ethyl O-4-nitrophenylethylphosphonate)

103 to 104

Sarin (isopropylmethylphosphonofluoridate)

1000

Phyllobates aurotaenia, a Colombian frogKokoe arrow poisonSeleno VE, Phospholine,…100 to 1000

Atelopus zeteki, a Panamanian arrow-poison frog.

Atelopidtoxin

Indian Cobra venomIndian Cobra neurotox.

Fugu, Puffer fishes and certain salamanders.

TetrodotoxinHomocholine Tammelin-ester.

Castor beans, Ricinus communisRicin, crystallineDioxine10 to 100

Clostridium tetani bacteriaTetanus toxin, crystalline10-3 to 10-2

Botulinum toxin type A. ClostridiumBotulinum bacteria

Botulinum toxin type A, αfraction

10-4 to 10-3

SourceName

Natural PoisonSynthetic PoisonRelative Lethality

Relative lethality based on published data


Challenges in Chemistry from vegetable oils

● Development of « Green » chemistry from vegetable oils requires to set the conditions to make money

● Use all parts of vegetable oils:● Glycerol● Fatty acids� high concentration in targeted fatty acid � dedicated vegetable oils

● Develop Safer processes

● Renewable chemicals with improved Life Cycle Analysis● Renewable (bio-based) # biodegradable # safe


Thank you for your attention

Documents

REFINERY OF THE FUTURE: FEEDSTOCK, PROCESSES, PRODUCTS ... · REFINERY OF THE FUTURE: FEEDSTOCK, PROCESSES, PRODUCTS Jean-Luc DUBOIS EuroBioRef Summer School Lecce, September 18th