The Biorefinery:Platform Chemical production from low cost sustainable raw

materialsDr Rafael Dr Rafael LuqueLuque

Green Chemistry Centre of ExcellenceGreen Chemistry Centre of ExcellenceUniversity of YorkUniversity of York

Outline• Introduction

• Catalysing change: unlocking the Biorefinery (feat. Starbon® acids)

• The biorefinery concept • Examples

• Integrated biorefinery

• Platform Chemical production from low-cost sustainable raw materials using Green Processing Strategies

• The project

•Alternative feedstocks and the biorefinery

• Upstream processing

• Bioreaction

• Downstream processing

• Platform molecules prod.

Alternative Feedstocks

BozellBozell, J.J.; , J.J.; HobergHoberg, J.O et el, , J.O et el, Green Chemistry Green Chemistry –– Frontiers in Benign Chemical Synthesis and ProcessesFrontiers in Benign Chemical Synthesis and Processes,,Oxford University PressOxford University Press, 1998, p.27, 1998, p.27--45.45.OkkerseOkkerse, C.; van , C.; van BekkumBekkum, H., , H., Green ChemistryGreen Chemistry, April 1999, p.107, April 1999, p.107--114.114.KlassKlass, D.L.; , D.L.; Biomass for renewable energy, fuels, and chemicalsBiomass for renewable energy, fuels, and chemicals, , Academic PressAcademic Press, , 19981998, p.91, p.91--157,p.495157,p.495--542. 542.

Carbon available in polymeric (cellulose, starch, lignin, proteiCarbon available in polymeric (cellulose, starch, lignin, protein) n) and and monomericmonomeric (carbohydrates, amino acids, pigments) forms (carbohydrates, amino acids, pigments) forms from biomass. The available biomass is sufficient to support foofrom biomass. The available biomass is sufficient to support food, d, energy and the chemical industry even in a 2040 scenario.energy and the chemical industry even in a 2040 scenario.

Biorefinery I

KammKamm, B.; , B.; KammKamm, M.; Gruber, P.R.; , M.; Gruber, P.R.; KromusKromus, S., , S., Biorefineries Biorefineries –– Industrial Processes and Products. Industrial Processes and Products. Status Quo and Future directionsStatus Quo and Future directions, , Wiley (2006)Wiley (2006), p.16, p.16--20.20.KlassKlass, D.L.; , D.L.; Biomass for renewable energy, fuels, and chemicalsBiomass for renewable energy, fuels, and chemicals, , Academic PressAcademic Press, , 19981998, p.91, p.91--157, p.495157, p.495--542. 542.

MittelbachMittelbach, M.; , M.; RemschmidtRemschmidt, C., , C., BiodieselBiodiesel –– the comprehensive handbookthe comprehensive handbook, , 2nd edition (2005).2nd edition (2005).

Biorefinery I

KammKamm, B.; , B.; KammKamm, M.; Gruber, P.R.; , M.; Gruber, P.R.; KromusKromus, S., , S., Biorefineries Biorefineries –– Industrial Processes and Products. Industrial Processes and Products. Status Quo and Future directionsStatus Quo and Future directions, , Wiley (2006)Wiley (2006), p.16, p.16--20.20.KlassKlass, D.L.; , D.L.; Biomass for renewable energy, fuels, and chemicalsBiomass for renewable energy, fuels, and chemicals, , Academic PressAcademic Press, , 19981998, p.91, p.91--157, p.495157, p.495--542. 542.

MittelbachMittelbach, M.; , M.; RemschmidtRemschmidt, C., , C., BiodieselBiodiesel –– the comprehensive handbookthe comprehensive handbook, , 2nd edition (2005).2nd edition (2005).

‘A biorefinery is a facility thatintegrates biomass conversionprocesses and equipment to

produce fuels, power and chemicalsfrom biomass. It is analogous to

todays petroleum refineries.

Biorefinery I

KammKamm, B.; , B.; KammKamm, M.; Gruber, P.R.; , M.; Gruber, P.R.; KromusKromus, S., , S., Biorefineries Biorefineries –– Industrial Processes and Products. Industrial Processes and Products. Status Quo and Future directionsStatus Quo and Future directions, , Wiley (2006)Wiley (2006), p.16, p.16--20.20.KlassKlass, D.L.; , D.L.; Biomass for renewable energy, fuels, and chemicalsBiomass for renewable energy, fuels, and chemicals, , Academic PressAcademic Press, , 19981998, p.91, p.91--157, p.495157, p.495--542. 542.

MittelbachMittelbach, M.; , M.; RemschmidtRemschmidt, C., , C., BiodieselBiodiesel –– the comprehensive handbookthe comprehensive handbook, , 2nd edition (2005).2nd edition (2005).

Forest biomass & woodwaste, grasses, other

cultivated crops, algae,water plants, municipaland agricultural waste

‘A biorefinery is a facility thatintegrates biomass conversionprocesses and equipment to

produce fuels, power and chemicalsfrom biomass. It is analogous to

todays petroleum refineries.

Biorefinery I

KammKamm, B.; , B.; KammKamm, M.; Gruber, P.R.; , M.; Gruber, P.R.; KromusKromus, S., , S., Biorefineries Biorefineries –– Industrial Processes and Products. Industrial Processes and Products. Status Quo and Future directionsStatus Quo and Future directions, , Wiley (2006)Wiley (2006), p.16, p.16--20.20.KlassKlass, D.L.; , D.L.; Biomass for renewable energy, fuels, and chemicalsBiomass for renewable energy, fuels, and chemicals, , Academic PressAcademic Press, , 19981998, p.91, p.91--157, p.495157, p.495--542. 542.

MittelbachMittelbach, M.; , M.; RemschmidtRemschmidt, C., , C., BiodieselBiodiesel –– the comprehensive handbookthe comprehensive handbook, , 2nd edition (2005).2nd edition (2005).

Production of biodiesel from trans-esterification of fats. Glycerol

(platform molecule) produced asby-product

Forest biomass & woodwaste, grasses, other

cultivated crops, algae,water plants, municipaland agricultural waste

‘A biorefinery is a facility thatintegrates biomass conversionprocesses and equipment to

produce fuels, power and chemicalsfrom biomass. It is analogous to

todays petroleum refineries.

Biorefinery II

Danner, H.; Braun, R., Chem. Soc. Rev., 28 (1999), p.395-405.Habova, V.; Melzoch, K. et el, Desalination, 163 (2004), p.361-372.

Biorefinery II

Danner, H.; Braun, R., Chem. Soc. Rev., 28 (1999), p.395-405.Habova, V.; Melzoch, K. et el, Desalination, 163 (2004), p.361-372.

Biorefinery II

2,3-butanediol produced from glucoseusing Klebsiella oxytoca,

acetaldehyde from glucose usingZymomonas mobilis, Succinic acid

from glucose using E.coli orActinobacillus succinogenes

Danner, H.; Braun, R., Chem. Soc. Rev., 28 (1999), p.395-405.Habova, V.; Melzoch, K. et el, Desalination, 163 (2004), p.361-372.

Biorefinery II

2,3-butanediol produced from glucoseusing Klebsiella oxytoca,

acetaldehyde from glucose usingZymomonas mobilis, Succinic acid

from glucose using E.coli orActinobacillus succinogenes

Danner, H.; Braun, R., Chem. Soc. Rev., 28 (1999), p.395-405.Habova, V.; Melzoch, K. et el, Desalination, 163 (2004), p.361-372.

Produced in a broth. SeparatedUsing electrodialysis with bi-Polar membranes (EDPM)

By B. A. Thorp

B26

7

8

9

10

Wheat

BioreactionDownstream processing

Platform chemicals

Derivatives

Upstream processing

Platform Chemical production from low-cost sustainable raw materials using Green Processing Strategies

Wheat BioreactionPlatform

Chemicals

Upstream processing

B26

7

8

9

10

Downstream processing

Filtrate

Solid

FlourHydrolysate

FungalAutolysate

Fungal fermentation

Autolysis

WheatHydrolysis

Flour

Upstream Processing

AspergillusAspergillusawamoriawamori

Crops

••Dry and Wet Milling Dry and Wet Milling ••Enzyme+ Acid Hydrolysis Enzyme+ Acid Hydrolysis ••Fungal Fungal fermferm. + hydrolysis. + hydrolysis(Filtrate)(Filtrate)••Fungal Fungal fermferm. +. + autolysisautolysis(solid)(solid)

Bioreaction

Wheat BioreactionPlatform

Chemicals

Upstream processing

B26

7

8

9

10

Downstream processing

Filtrate

Solid

FlourHydrolysate

FungalAutolysate

Fungal fermentation

Autolysis

WheatHydrolysis

Flour

Upstream Processing

AspergillusAspergillusawamoriawamori

Crops

••Dry and Wet Milling Dry and Wet Milling ••Enzyme+ Acid Hydrolysis Enzyme+ Acid Hydrolysis ••Fungal Fungal fermferm. + hydrolysis. + hydrolysis(Filtrate)(Filtrate)••Fungal Fungal fermferm. +. + autolysisautolysis(solid)(solid)

Bioreaction

Nu

trie

nts

rese

rvoi

rFlourHydrolysate

FungalAutolysate

B26

7

8

9

10

CropsBioreaction Downstream

processingPlatform

Chemicals

Upstream processing

CO2

A. succinogenes slope inoculum

Broth

NaOH

Bioreaction

B26

7

8

9

10

Nu

trie

nts

rese

rvoi

rFlourHydrolysate

FungalAutolysate

B26

7

8

9

10

CropsBioreaction Downstream

processingPlatform

Chemicals

Upstream processing

CO2

A. succinogenes slope inoculum

Broth

NaOH

Bioreaction

Downstream processing

B26

7

8

9

10

EXPERIMENTAL SETUPKey factors

• Requirement– CO2 feed in– pH control – Temp. control– Shaking – Sterilisation

EXPERIMENTAL SETUPKey factors

• Requirement– CO2 feed in– pH control – Temp. control– Shaking – Sterilisation

EXPERIMENTAL SETUPKey factors

• Requirement– CO2 feed in– pH control – Temp. control– Shaking – Sterilisation

EXPERIMENTAL SETUPKey factors

• Requirement– CO2 feed in– pH control – Temp. control– Shaking – Sterilisation

EXPERIMENTAL SETUPKey factors

• Requirement– CO2 feed in– pH control – Temp. control– Shaking – Sterilisation

EXPERIMENTAL SETUPKey factors

• Requirement– CO2 feed in– pH control – Temp. control– Shaking – Sterilisation

0 10 20 30 40 50 60 70 80

0

10

20

30

40

0

2

4

6

8 Succinic acid

Suc

cini

c ac

id (g

/L)

Time (h)

OD

OD

660

WheatBioreaction

Platform Chemicals

Upstream processing

B26

7

8

9

10

Downstream processing

Filtration

Solid

Neutralisation

Separation

Different pH

Broth

Downstream ProcessingFiltration/Separation/Neutralisation

Downstream processing

B26

7

8

9

10

Supernatant

••EBPMEBPM••CrystallisationCrystallisation••Extraction by ionic liquidsExtraction by ionic liquids••Reactive extractionReactive extraction••VaccuumVaccuum distilationdistilation……

WheatBioreaction

Platform Chemicals

Upstream processing

B26

7

8

9

10

Downstream processing

Filtration

Solid

Neutralisation

Separation

Different pH

Broth

Downstream ProcessingFiltration/Separation/Neutralisation

Downstream processing

B26

7

8

9

10

Supernatant

••EBPMEBPM••CrystallisationCrystallisation••Extraction by ionic liquidsExtraction by ionic liquids••Reactive extractionReactive extraction••VaccuumVaccuum distilationdistilation……

Platform Chemicals

WheatBioreaction Platform

Chemicals

Upstream processing

B26

7

8

9

10

Downstream processing

Platform chemicals

Platform Chemicals

GreenConversions

HeterogeneousCatalysis Microwave

ReactorsMembraneReactors

Water as aSolvent

scCO2 andnear scCO2

Microwave& Ultrasound

STARBON®

WheatBioreaction Platform

Chemicals

Upstream processing

B26

7

8

9

10

Downstream processing

Platform chemicals

Platform Chemicals

GreenConversions

HeterogeneousCatalysis Microwave

ReactorsMembraneReactors

Water as aSolvent

scCO2 andnear scCO2

Microwave& Ultrasound

STARBON®Derivatives

Platform Molecules

U.S Department of Energy, U.S Department of Energy, Top Value Added Chemicals From BiomassTop Value Added Chemicals From Biomass, , August 2004August 2004..BozellBozell, J.J.; , J.J.; MoensMoens, L.; Elliott, D.C. et al.; , L.; Elliott, D.C. et al.; Resources, conservation and recycling, 28 (2000),Resources, conservation and recycling, 28 (2000), p.227p.227--239.239.

Platform Molecules

U.S Department of Energy, U.S Department of Energy, Top Value Added Chemicals From BiomassTop Value Added Chemicals From Biomass, , August 2004August 2004..BozellBozell, J.J.; , J.J.; MoensMoens, L.; Elliott, D.C. et al.; , L.; Elliott, D.C. et al.; Resources, conservation and recycling, 28 (2000),Resources, conservation and recycling, 28 (2000), p.227p.227--239.239.

Levulinic acid can be produced frombiomass then used to produce key

chemicals such as methyltetra-hydrofuran (MTHF) amongst others(automobile fuel extender, solvent).

Platform Molecules

U.S Department of Energy, U.S Department of Energy, Top Value Added Chemicals From BiomassTop Value Added Chemicals From Biomass, , August 2004August 2004..BozellBozell, J.J.; , J.J.; MoensMoens, L.; Elliott, D.C. et al.; , L.; Elliott, D.C. et al.; Resources, conservation and recycling, 28 (2000),Resources, conservation and recycling, 28 (2000), p.227p.227--239.239.

Levulinic acid can be produced frombiomass then used to produce key

chemicals such as methyltetra-hydrofuran (MTHF) amongst others(automobile fuel extender, solvent).

BournayBournay, L.; , L.; CasanaveCasanave, D.; , D.; DelfortDelfort, B. et el, , B. et el, Catalysis Today, 106 (2005),Catalysis Today, 106 (2005), p.190p.190--192.192.PoteraPotera, C., , C., Environ. Health Perspective, 113 (Dec 2005),Environ. Health Perspective, 113 (Dec 2005), p.832p.832--835835..

Platform Molecules II

BournayBournay, L.; , L.; CasanaveCasanave, D.; , D.; DelfortDelfort, B. et el, , B. et el, Catalysis Today, 106 (2005),Catalysis Today, 106 (2005), p.190p.190--192.192.PoteraPotera, C., , C., Environ. Health Perspective, 113 (Dec 2005),Environ. Health Perspective, 113 (Dec 2005), p.832p.832--835835..

Glycerol can be used toproduce propandiols,

propanol, glyceric acid,glyerates (mono, tri or di),

glycidol and branchedpolymers (including

dendrimers) etc.

Platform Molecules II

BournayBournay, L.; , L.; CasanaveCasanave, D.; , D.; DelfortDelfort, B. et el, , B. et el, Catalysis Today, 106 (2005),Catalysis Today, 106 (2005), p.190p.190--192.192.PoteraPotera, C., , C., Environ. Health Perspective, 113 (Dec 2005),Environ. Health Perspective, 113 (Dec 2005), p.832p.832--835835..

Glycerol can be used toproduce propandiols,

propanol, glyceric acid,glyerates (mono, tri or di),

glycidol and branchedpolymers (including

dendrimers) etc.

Succinic acid formallyproduced from maleic

anhydride derived frompetroleum. Can now bemade from glucose in a

biorefinery and utilised fornumerous applications

Platform Molecules II

0

25

50

75

100

30 min 2 h 4 h

SA CONVERSION SEL. MES0

25

50

75

100

30 min 2 h 4 h

SA CONVERSION SEL. MES

STARBONSTARBON®®

3 mL FBroth30 mmol EtOH

0.1 g STARBON85o C HClHCl/H/H22SOSO44

ESTERIFICATION OF SUCCINIC ACID (SA) WITH ETHANOL

Starbon® catalyst is as good as conc. sulfuric acid(even slightly better as the rate of formation of the diester is 5 times slower!!).

equimolar mono-+diester (4h)

0

25

50

75

100

1 use 2 use 3 use

3 mL FBroth30 mmol EtOH

0.1 g STARBON®85o C

CATALYST REUSE

4 h reaction

SA C

onve

rsion

(mol%)

Starbon® acids are stable enough (3 uses) but their stability can be improved (ongoing studies)

Acknowledgments

Prof. James ClarkProf. James Clark

DrDr DuncanDuncan MacquarrieMacquarrie

DrDr VitaliyVitaliy BudarinBudarin

Tom FarmerTom Farmer

Prof. ColinProf. Colin WebbWebb

DrDr ChenyuChenyu DuDuCarolCarol LinLin

DrDr RuohangRuohang WangWang

MANY THANKS MANY THANKS FOR YOUR KIND ATTENTIONFOR YOUR KIND ATTENTION

Questions?