platform chemicals from renewable raw materials

Platform Molecules and Green Chemistry

Platform Chemicals From Renewable Raw Materials

Professor Colin WebbSatake Centre for Grain Process Engineering

School of Chemical Engineering and Analytical ScienceThe University of Manchester

Renewable Resources & Biorefineries Conference, September 6–8, 2006, York

RRB2, York, September 2006

Raw Materials, Agriculture and Chemistry

“Petrochemical processes have provided low cost production routes for fuels, plastics and chemicals for well over 50 years but the escalating impact on the environment and the inevitable future depletion of fossil feedstocks make it essential that benign, sustainable, alternatives be developed commercially in the very near future.”

RSC, 2003


Renewable raw materials

Photosynthetic biomassStarchy cropsSugar cropsOil seedsLignocellulosics

Water

Atmospheric gases (e.g. CO2, methane)


Platform chemicals from petroleum

Crude oilJet fuel Light fuel/diesel oil

Natural gas liquids (methane, ethane,

propane)

Naphtha Oil coke

Heavy fuel oil

Ethylene79 x109 kg

$0.6/kg

Propylene43.1x 109 kg

$0.44/kg

BTXMixture Butane/enes

Butadiene8.5 x109 kg

$0.57/kg

Polybutadiene1.82 x109 kg

MTBE22.2 x109 kg

$0.29/kg

Acrylonitrile4.3?109 kg$1.98/kg

Propylene oxide

4?109 kg$1.41/kg

Acrylic acid2?109 kg$1.92/kg

Isopropanol2.3?109 kg$0.84/kg

n-Butanols1.78?109 kg Polypropylene

<$1/kg

Propylene glycol

0.97?109 kg$1.48/kg

Acrylic fibres, nitrilerubber,

ABS, SAN

Benzene20.79?109 kg

$0.33/kg

o-/m-/p-xylenes10.1?109 kg$0.31/kg

Toluene7.85?109 kg

$0.33/kg

Terephthalicacid3.2?109 kg$0.63/kg

Ethylbenzene19.7?109 kg$0.56/kg

Cumene8?109 kg$0.56/kgCyclohexane

5.1?109 kg$0.44/kg

Diisocyanates2.23?109 kg

$2.2/kg

Styrene19.2?109 kg$0.55/kg

Polystyrene, SBR, ABS,

SAN, resins

Phenol3.4?109 kg$0.82/kg

Acetone3.4?109 kg$0.46/kg

Cyclohexanone,Nylon-6,6

Methanol29.1?109 kg

$0.21/kg

Acetic acid6?109 kg$0.99/kg

Formaldehyde4.9?109 kg$0.46/kg

Vinyl chloride

24?109 kg$0.48/kg

Ethylene oxide11.2?109 kg

$1.17/kg

Vinyl acetate3.8?109 kg

$1.1/kg

Ethanol2.6?109 kg$0.42/kg

Polyethylene<$1/kg

Polyvinyl chloride

Ethylene glycol9.7?109 kg$0.53/kg

Ethanolamines0.84?109 kg

$1.28/kg

Crude oilJet fuelJet fuel Light fuel/diesel oil

Light fuel/diesel oil

Natural gas liquids (methane, ethane,

propane)

Naphtha Oil cokeNatural gas liquids (methane, ethane,

propane)

Naphtha Oil coke

Heavy fuel oilHeavy fuel oil

BTX


Propylene oxide

4?109 kg$1.41/kg




<$1/kg

Propylene glycol

0.97?109 kg$1.48/kg


ABS, SAN


Propylene oxide

4?109 kg$1.41/kg




<$1/kg

Propylene glycol

0.97?109 kg$1.48/kg


ABS, SAN

Benzene20.79?109 kg

$0.33/kg


Toluene7.85?109 kg

$0.33/kg




5.1?109 kg$0.44/kg


$2.2/kg



SAN, resins




Benzene20.79?109 kg

$0.33/kg


Toluene7.85?109 kg

$0.33/kg




5.1?109 kg$0.44/kg


$2.2/kg



SAN, resins




Methanol29.1?109 kg

$0.21/kg



Methanol29.1?109 kg

$0.21/kg



Vinyl chloride

24?109 kg$0.48/kg


$1.17/kg


$1.1/kg


Polyethylene<$1/kg

Polyvinyl chloride



$1.28/kg

Vinyl chloride

24?109 kg$0.48/kg


$1.17/kg


$1.1/kg


Polyethylene<$1/kg

Polyvinyl chloride



$1.28/kg


New products or new processes?

ConventionalProduct

Replacement

Sustainable Raw Material New Process

ConventionalProcess

Sustainable Raw Material

AlternativeProducts

AlternativeProductsNew ProcessSustainable

Raw Material


Bioprocessing

Bioprocessing will lead to more natural and cost-effective means of converting natural feedstocks into platformchemicals

Platform chemicals that can be produced in large quantities by microorganisms include acetic acid, ethanol, glycerol, succinicacid, pyruvic acid, 2,3-butanediol and 1,3-propanediol

They are different from current petrochemical building blocks (e.g. ethylene, propylene and butadiene) and therefore require significant technological research

Benefit will come from collaboration of chemists, biotechnologists and (bio)chemical-engineers


Cereals as a Renewable Resource

Sustainable renewable chemicals will have to come mostly through photosynthesisThe most intensive crops are those based on starch (10 times more chemical energy is stored as cereal grain starch than as sucrose)50% of the world’s food is cereal basedCereal processing for human consumption leaves approximately 15% of the grain as waste productLarge amounts of cereal grain are also wasted through poor post-harvest techniquesand…yields are still increasing


Cereal Grain or Whole Crop?

For every tonne of grain most cereals produce approximately one tonne of straw and other residues

Ligno-cellulosic material is much more difficult to process than starchy material

Straw has a bulk density 1/15th of that of grain

Biorefinery processing of straw is currently not feasible

Like petroleum refining we should start simple (glucose cf. gasoline; lignocellulose cf. bitumen)


Chemical Products From Glucose

GLUCOSE

2,3-BUTANEDIOL

LACTIC ACID

ACETONE

BUTANOL

ACETIC ACID

ETHANOL

SORBITOL

HYDROXYMETHYLFURFURAL

Glycerol

SCP

BUTANEDIOL ACETATEMETHYL ETHYL KETONEMETHYL VINYL KETONE

BUTADIENE

POLYBUTADIENE

ACRYLATE RESINS

BISPHENOL AMETHYL iso-BUTYL KETONEMETHYL METHACRYLATE

POLYCARBONATE RESINS

DIBUTYL PHTHALATE PVC RESINS

DIMETHYL TEREPHTHALATEACETIC RESINS

ETHYLENEETHANOLAMINESBUTADIENE

POLYETHYLENEVINYL ACETATESTYRENEACETALDEHYDEETHYLENE GLYCOLDRUGS

POLYURETHANESSURFACTANTS

TEREPHTHALIC ACID

GLUCOSE

2,3-BUTANEDIOL

LACTIC ACID

ACETONE

BUTANOL

ACETIC ACID

ETHANOL

SORBITOL


2,3-BUTANEDIOL

LACTIC ACID

ACETONE

BUTANOL

ACETIC ACID

ETHANOL

SORBITOL


Glycerol

SCP



BUTADIENE

POLYBUTADIENE

ACRYLATE RESINS



POLYCARBONATE RESINS

DIBUTYL PHTHALATE PVC RESINS

DIMETHYL TEREPHTHALATEACETIC RESINSDIMETHYL TEREPHTHALATEACETIC RESINS



POLYETHYLENEVINYL ACETATESTYRENEACETALDEHYDEETHYLENE GLYCOL

POLYETHYLENEVINYL ACETATESTYRENEACETALDEHYDEETHYLENE GLYCOLDRUGS

POLYURETHANESSURFACTANTS

DRUGSPOLYURETHANESSURFACTANTS

TEREPHTHALIC ACID


Top 12 Sugar-based Building Blocks

Glutamic acidGlycerolItaconic acidLevulinic acidSorbitolXylitol/arabinitol

Glucaric acidAspartic acid3-hydroxy propionic acid3-hydroxybutyrolactone2,5-furan dicarboxylic acid1,4 succinic, fumaric and malic acids


Succinic Acid

C4H6O4; MW = 118.09 Butanedioic acid; 1,2-ethandicarboxylic acid; dihydrofumaric acid and amber acid Important intermediate in the manufacture of:

pharmaceuticals, elastomers, protective coatings, electrical insulations, foods, detergents, surfactants, corrosion inhibitors and cosmetics with a total market size of more than $400,000,000 p a.

Currently produced from petrochemical feedstocks (butane - maleic anhydride - succinic acid)Bioproduction could decrease production cost from $7/kg to $0.6/kg


Succinic Acid Derivatives

OH

O

OH

O

Succinic acid

OHOH

1,4-Butanediol (BDO)Solvent

O

NH 2

O

N H 2

SuccindiamidePBS Polymer

O O

γ-Butyrolactone (GBL)SolventO

Tetrahydrofuran (THF)Solvent

O NH

2-PyrrolidoneSolvent

O NCH3

N-Methyl Pyrrolidone (NMP)Solvent

O

O

O

O

CH3CH3

Dibasic Ester (DBE)Solvent, polymer

NH2

NH2

1,4-DiaminobutanePolyamide 46 (Nylon)

CNCN

SuccinonitrileResin


Bioconversion of glucose to Succinic acid

Actinobacillus succinogenes:Gram-negative facultatively anaerobic bacterium isolated from bovine rumen in 1999Moderate halophile & osmophileCapnophilic & aerotolerantCan use both pentose and hexose sugars Natural succinate producer Produces succinate mainly via a single pathwayConsumes CO2 as part of the production process


Metabolic Pathway

Succinate

Glucose-6P

PEP

Acetyl-coA

Acetate

Pyruvate

α-KetoglutarateCitrate

OAA

Malate

H: reducing power

CO2 2H2H

2H CO2

2H

Fumarate

4H

outLactate

Ethanol outout

Out

4H

outCO2 in

Glucose


Current raw material - Medium 1

US Patent5,573,931

Glucose

Yeast Extract

B12BiotinFolic acidRiboflavinNiacinPantothenate (B5)p-aminobenzoateThiaminePyridoxine (B6)

Vitamins

MineralsNaClNaH2P4∙H2ONa2HP4CaCl2∙2H2OMgCl2∙6H2O


Bioconversion of Cereals to Succinic Acid

Wheat

Bioreaction Downstream processing Succinic

acid

Derivatives

Upstream processing



Wheat


acid

Derivatives

Upstream processing

Starch 620000 - 750000 Na 30 B1 5.4N 2006 Cu 4.5 B2 1.1P 3400 Cd 0.1 B3 110S 912 - 1995 Cr 0.4 B6 3.3

Mg 1589 Pb 1 E 54Fe 37 Ni 0.3K 4180 Mn 35Ca 390 Sn 7.9

Zn 5

Macronutrients Micronutrients Vitamins

(µg g-1, db) (µg g-1, db) (µg g-1, db)

contains all nutrients generally required for bioprocessing



Wheat


acid

Derivatives

Upstream processing

Starch 620000 - 750000 Na 30 B1 5.4N 2006 Cu 4.5 B2 1.1P 3400 Cd 0.1 B3 110S 912 - 1995 Cr 0.4 B6 3.3

Mg 1589 Pb 1 E 54Fe 37 Ni 0.3K 4180 Mn 35Ca 390 Sn 7.9

Zn 5

Macronutrients Micronutrients Vitamins

(µg g-1, db) (µg g-1, db) (µg g-1, db)

contains all nutrients generally required for bioprocessing

…but not in a directly accessible form:

The carbon source is mostly in the form of starch

most fermentations require simpler sugars

Likewise most of the Nitrogen is in the form of proteins

most fermentations require free amino acids

Some pre-processing is therefore required


Upstream ProcessingUpstream processing

Bioreaction Downstream processingWheat

Succinicacid

B26

7

8

9

10

Glucoserich

Nitrogenrich

Filtrate

Solid

FlourHydrolysate

Fungal Autolysate

Fungal fermentation

Autolysis

WheatHydrolysis

Flour

Aspergillus Aspergillus awamoriawamori

Generic feedstock


Upstream processing

Yeast Extract: 5 g/LFAN: 0.925 g/L

(Equiv. to 18.5 g/L Yeast Extract)

Autolysate N source

C source Glucose: 50 g/LGlucose: 335 g/LHydrolysate

Succinic acid fermentation requires

Generic feedstockprovides


BioreactionUpstream processing

Bioreaction Downstream processingWheat

Succinicacid

B26

7

8

9

10

Gen

eric

feed

stoc

k

B26

7

8

9

10

FlourHydrolysate

Cell Autolysate

CO2

A. succinogenes slope inoculum

Broth

NaOH


Bioreaction

Small anaerobic bioreactors with gas distributor 1 L bench-top bioreactor

COCO22 feed in feed in pH control pH control Temperature controlTemperature controlShaking Shaking SterilisationSterilisation


Batch fermentation

-

5

10

15

20

25

30

35

40

45

0 5 10 15 20 25 30

Fermentation time (hours)

Con

cent

ratio

n (g

/L)

0

1

2

3

4

5

6

7

OD 66

0

GlucoseSuccinicOD660

-

5

10

15

20

25

30

0 10 20 30

Fermentation Time (hours)

Con

cent

ratio

n (g

/L)

Pyruvic acidSuccinic acidFormic acidAcetic acid


Summary of Batch Bioreactions

ConsumedInitial

55*71* 106303047*

30

505844*

(g/L)

Glucose

(g/L/h)(g/L)Y/NY/N(g/L)

YYYYYY

N

NNN

pHcontrol

0.31 0.56 0.41 0.54

-1.01

0.03

0.12 0.00 0.01

Product-ivity

0.73 0.82 0.53 0.65

-0.65

0.06

0.41 0.00 0.01

Yield

17.14.35N231035.67.28N43.4930.65.41Y58819.65.45Y307

00.52N-627.26.09Y425

1.091.79N184

6.152.65N15301.39N302

0.285.5N441

SAOD660VitaminsNo.


Succinic acid production

0

10

20

30

40

1 2 3 4 5 6 7 8 9 100

10

20

30

40S

ucci

nic

acid

(g/L

)

Batch number

No pH control


Can a cereal based medium replace Medium 1?

US Patent5,573,931

Glucose

Yeast Extract


HydrolysateVitamins

Can flour hydrolysatereplace glucose?



Testing the flour hydrolysate

0

10

20

30

40

1 2 3 4 5 6 7 8 9 100

10

20

30

40S

ucci

nic

acid

(g/L

)

Batch number

No pH control

Flou

r hy

drolys

ate

Commer

cial g

luco

se



US Patent5,573,931

Glucose

Yeast Extract


HydrolysateVitamins


Can flour hydrolysatereplace vitamins?



0

10

20

30

40

1 2 3 4 5 6 7 8 9 100

10

20

30

40S

ucci

nic

acid

(g/L

)

Batch number

Testing the flour hydrolysateMedium 1 without vitamins

Medium 1 with vitamins

Hydrolysate without vitamins

No pH control



GlucoseHydrolysate US Patent5,573,931

Yeast Extract

HydrolysateB12BiotinFolic acidRiboflavinNiacinPantothenate (B5)p-aminobenzoateThiaminePyridoxine (B6)

Vitamins



MineralsCan fungal autolysatereplace Yeast Extract

and minerals?

NaClNaH2P4∙H2ONa2HP4CaCl2∙2H2OMgCl2∙6H2O


The generic feedstock as sole nutrient

0

10

20

30

40

1 2 3 4 5 6 7 8 9 100

10

20

30

40S

ucci

nic

acid

(g/L

)

Batch number

Only hydrolysate + autolysate

No pH control



GlucoseHydrolysate US Patent5,573,931

Yeast Extract

NaClNaH2P4∙H2ONa2HP4CaCl2∙2H2OMgCl2∙6H2O

Minerals



Can fungal autolysatereplace Yeast Extract

and minerals?

Hydrolysate AutolysateAutolysate



US Patent5,573,931

Hydrolysate




and minerals?

Autolysate

Hydrolysate

Autolysate



US Patent5,573,931

Hydrolysate

AutolysateN

Y/N

YE

0.730.31 17.14.35YNN20055*10

(g/L/h)(g/L)Y/NY/NY/N(mg/L)(g/L)

YieldProductivitySAOD660pH controlMineralsVitaminsFANGlucoseBatch

N

Y/N

YE

0.730.31 17.14.35YNN20055*10



Hydrolysate


Autolysate



and minerals?



US Patent5,573,931




and minerals?

0 20 40 60

0

5

10

15

20

-1

0

1

2

3

4

5

Succinic acidS

ucci

nic

acid

(g/L

)

Time (h)

OD

OD

660

Hydrolysate

Autolysate

AutolysateN

Y/N

YE

0.730.31 17.14.35YNN20055*10



N

Y/N

YE

0.730.31 17.14.35YNN20055*10



Hydrolysate


Downstream ProcessingUpstream processing

Bioreaction Downstream processing

SuccinicacidWheat

Crystallisation

Extraction by ionic liquids

Adsorption

Electrodialysis with bipolar membranes (EDBM)

Reactive extraction, vacuum distillation and crystallisation

B26

7

8

9

10


Conclusions

Key factors influencing bioproduction of succinic acid:Micro-organism, pre-culture, pH control, Vitamins

Achieved a succinic acid production of 35.6 g/L, with a yield of 0.82 g SA/g glucose.

It is possible to produce SA using only flourhydrolysate and fungal autolysate from wheat grain processing.

Platform chemicals can be produced from renewable resources


Acknowledgements

Miss Carol Lin

Dr Chenyu Du

Dr Apostolis Koutinas

Dr Ruohang Wang

platform chemicals from renewable raw materials

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