Jacco van Haveren

Programme Manager Chemicals

Wageningen University and Research Center/Biobased Products

Biobased chemicals and materials

Master Class, Terneuzen, 10 November, 2011

Existing and future biorefineries will produce feedstocks for

biobased chemicals and materials

Biorefineries

Usage of bulk (platform) chemicals

Bulk chemicals are used as:

Solvents

Starting components for soaps, lubricants, additives

(low molecular weight components)

Mostly as building blocks for polymers (high molecular

weight components) and hence materials

Building blocks can be either aliphatic (flexible) or

aromatic (rigid) nature

C6, C7, C8 (B, T, X)

C2

C3

C4

others (including MTBE)

4

Introduction

McKinsey: Innovation potential of fossil building blocks appears largely exploited

Most chemicals end up in polymeric materials

Consumption of thermoplastics in

Western Europe

PE

PP

PVC

PS/EPS

PET

others

About 50.000.000 tonnes in 2010

About ¾ of volume is in commodities like PE, PP, PVC

About 50 % of economic value is in other polymers!

Functionalised chemicals; C, H. N, O

Biobased

ambition

Biobased chemicals can have

Have a unique structure

Same structure as fossil oil based chemicals

Naturally occurring biopolymers will increase in importance, but developing biobased monomers for controlled polymerisation into biobased polymers will be the dominant development direction for replacing petrochemical based materials, e.g.

Compare starch based plastic versus PLA

Biomass based chemicals preferably should result from waste streams or crops avoiding food vs. non–food use competition

Biomass based monomers and polymers

Cellulose

Oils

Hemi-

cellulose

Lignin

Proteins

Cellulose (circa 50%): polymer of β-(1,4)-glucan

Hemi-cellulose (circa 25%): short-chain branched,

substituted polymer of C5 and C6 sugars

Lignin (circa 25%): polymer derived from

coniferyl, coumaryl and sinapyl alcohol precursors

Proteins (up to 10%, depending on the plant species):

polymer of amino acids

Oils (up to 10%, depending on the plant species):

e.g. esters of glycerine and fatty acids

Biomass composition

Oleochemie: vele toepassingen

J. Bozell, Oleochemicals as a Feedstock for the Biorefinery: High Value Products from Fats and Oils, Biorenewables Initiative Publications, Iowa State University, IA (2004).

Toepassingen van vetzuren in de VS in 2000

Building blocks for nylons from castor oil

Arkema Arkema

Automotive22%

Coatings8%

Construction16%

Footwear4%

Furniture34%

Thermal insulation

11%

Other5%

Automotive18%

Coatings15%

Construction18%Footwear

4%

Furniture29%

Thermal insulation

11%

Other5%

Building blocks for polyurethanes form vegetable oils

Total market (1985): 3.3 million tonnes Total market (2000): 9.3 million tonnes

Building blocks for polyurethanes from vegetable oils

Polyols produced by e.g. Cargill, Cognis

Building blocks for polyurethanes form vegetable oils Hydroformylation method for preparing vegetable oil based polyols;

DOW Chemical’s Renuva Polyol Technology

Novel renewable polyamides and non-isocyanate

polyurethanes for coating applications (NOPANIC):

Cooperation:

Nuplex Resins, CRODA, AKZONobel, Ursa Paint, TU/Eindhoven, WUR/FBR,

University of Utrecht

Target: • To develop scientific and applied knowledge for the generation of isocyanate free polyurethanes

Intended application area:

(Car refinish) Coatings

Potential spin off application:

Insulation materials, construction materials

Non-isocyanate polyurethanes

Cooperation: Nuplex Resins, NPSP, Cosun, Cargill, Calendula Oil, WUR/FBR, RUG

Target: To develop scientific and applied knowledge for the generation of well

functioning composite resins based upon (styrene-free) unsaturated polyesters can be generated.

Intended application area: Renewable based composite resins to be used in

e.g. wind turbine blades, train noses, automotive sector,

road signs, boats

Biobased composite resins

Fully renewable based alkyd resins

Alkyds for decorative paint:

• Solvent or waterborne

Oil: soya, safflower, sunflower, TOFA, etc.

• High extent of C18:2 offers the optimal properties

• Oil length: 35 - 85 % (renewable)

• poly-alcohols: glycerol, (di)pentaerythritol, trimethylol propane, etc

• poly-acids: (iso-, tere-, tetrahydro-)phthalic acid, trimellitic, etc

• Drying: Usually accelerated by cobalt or manganese based catalysts

•

Background

O O

OO

O

O

RO

Starting material

Sucrose

100 % renewable alkyd resins

Sucrose produced from sugar beet or sugar cane by

many companies including Sensus (Neth.) and Orafti

(Belgium)

Current estimated production volume: 140 million

tonnes/annum

O

OH

OH

HOHO

OO

OH

HO

HO

HO

H

Oligomeric sucrose-linoleate

binders:

Parameters varied: type of chain extender/ratio chain extender/FAME

additional acetylation

processing method; trans - or interesterification

100 % renewable alkyd resins

Sucrose based alkyd resins Test OVN-227 OVN-228 OVN-231

Comm.

product

Low shear viscosity

(dPa.s)14.0 14.0 13.8

High shear viscosity

(dPa.s)9.8 > 10 9.6 4.6

Solids (%) 89.6 93.7 85.7 80.5

VOC (g / L) 134 83 180 260

Whiteness 77.1 75.4 74.8 76.5

Drying (RT; 50 % RV) 0 0 0 0

Drying (5°C; 90 % RV) 0 0 0 0

Gloss 98.8 88.9 83.5 85.9

Water sensitivity

(4 days)0 0 0 0

Levelling 0 - 1 0 - 1 0 - 1 1 - 2

Hiding power 1 1 1 1

100 % renewable alkyd resins

• As latex (in water)

• As high solid paints (low VOC)

• Very flexible, high gloss, strong adhesion

• Drying times need to be evaluated in presence metal driers

Adhesion and flexibility test

Renewable alkyd resins produced by biotechnology

Alternative vegetable / FA sources: algae

AlgiCoat project

CO2

heat

other chemicals algae

Delesto (AkzoNobel/Essent)

Ingrepro / Wageningen UR

polyunsaturated

fatty acids

Wageningen

UR

residue

AkzoNobel

Delfzijl other products,

heat, electricity

other fatty

acids

Alternative renewable feedstocks

Chemicals from glycerol

coatings

polymeren

oplosmiddelen

antivries

koelvloeistof

polyesters

plastics

oplosmiddelen

coatings

polymeren

epoxyharsen

Dupont

ADM DOW, Solvay

FBR

Arkema

Top 12 chemicals from biomass (2004 US-DOE study)

Based on 2nd approach

Scientific fundamentals for certain choices are questionable

HO

OH

OH

OH

OHOH

HO OHHO

OOO

HO

O

O

HO

O

OHO

OH

NH2

O

HO

NH2

O

HO

O

OH

HO OH

O O

O

HO

O

OH

O

HO

O

OH HO OH

OCOOH

OHOOC

OH

OH

OH

OH

OHHO

OH

OH

OH

OH O

OH

O

HO

12

1 2 3

4 5 6 7

8 9 10 11

Biomass based monomers and polymers

Biobased Monomers

Target chemicals:

Functionalised chemicals

• Flexible diols, diacids, hydroxy acids predominantly produced by

biotechnology;

– Such chemicals can substitute current petrochemical based diols/diacids

and potentially olefines

• Rigid building blocks, by chemical conversion, to substitute petrochemical

based aromatics

Biobased Monomers

Scientific challenges:

Creating chemicals from fossil oil based feed stocks is about

selectively introducing functionality

Creating chemicals based upon biomass is about selectively

removing functionality • Dehydratation

• Deoxygenation

• Decarboxylation, decarbonylation

Some current monomers for polymers

Potential renewable based monomers

New building blocks- lactic acid

Now large scale production by NatureWorks; 140kt/a name plate capacity [PET production 2008 will be approx 49 MioT]

Application fields expanded to all kinds of biodegradable materials

Packaging films

Disposable containers (bottles, cups)

Fibres (textile)

Number of applications limited due to low Tg of approx. 60 °C

Innovations required for real brake-through

PLA; Effect of Chain Structure on Properties

PLA Biomaterials grade

Homopolymer of L-isomer

High melting point

In practice semi-crystalline

Transparent / Hazy

PLA Packaging grade

Copolymer of L- and D-isomers

Low melting point

In practice amorphous

Transparent

Processing: 3D-foamed structures

Expandable bead technique

Good cell structure

Density <30 g/l

Rigid biobased building blocks: sorbitol and isosorbide

What is dianhydrosorbitol or isosorbide?

Isosorbide is prepared by acid catalysed dehydration of sorbitol

Sorbitol is prepared by hydrogenation of glucose, which can be

prepared by hydrolysis of starch

Routes to isosorbide starting from cellulose are being developed

O

O

OH

HO

OOHO

CH2OH

OHO

H

n

OHO

CH2OH

OH

H

OH

HOHO

OH

OH OH

OHOH

starch glucose sorbitol isosorbide

Heavy metal free heat stabilisation of PVC

Target; replace lead stabilisers

Alternative to tin based stabilisers?

• effect of different types of stabilisers on early colour and

long term heat stability

• HMF compound (min), SHS (Mathis oven, 200 °C, 30 min)

lead compound

HMF blank

+ uracil (0.15 phr)

+ BGAC (0.2 phr)

Effects of polyols on early

colour of HMF PVC

compound

• Polyols were added

based on mmol

primary hydroxyl

groups:

– sorbitol and

glycerol: 20

mmol

– TMP: 13 mmol

t in m

in. @

200 °C

in M

ath

is o

ven

0

30

blank sorbitol TMP glycerol

Natural polyols as heat stabilisers

Heavy metal free heat stabilisation of PVC

AKZO-ATO joint development (WO0206392)

• monomeric dihydropyridines as colour stabilisers

• work via curative mechanism; reduction of polyene sequences

• synergistic relationship with polyols, especially sorbitol, and inorganic

acid scavengers

• some were already known and available (D507, Sinesal-M), yet

expensive and unstable

N

O

O

O

O

H

RR

Dominant current plasticisers are esters of

phthalic acid: e.g. DEHP,DINP

Phthalates are potential endocrine

disruptors

Isosorbide plasticisers are esters of

dianhydro sorbitol, or isosorbide: e.g.

IsDEH (DEHP analogue)

O

OO

O O

O

O

O

O

O

Isosorbide based plasticisers

Plasticisers for poly (vinyl chloride):

Phthalates: 80-90% of all plasticisers

DEHP (DOP) BBP

Phthalates are under environmental pressure:

need for non-toxic, environmentally benign and commercially viable alternatives.

O

O

O

O

O

O

O

O

Isosorbide; alternative plasticisers

Isosorbide diesters

O

OO

O O

O+ 2 HO

O

+ 4 H2OHOOH

OH OH

OHOH

Directly from sorbitol:

D.S. van Es et al., “Synthesis of Anhydroglycitol esters of improved colour”, WO

01/83488 to WUR/A&F

• Selective dehydration of sorbitol to isosorbide at 120 °C

• Esterification at 140-150 °C

• Macroporous ion exchange (Amberlyst 15) resin as catalyst

• Diester yields 95-99 %

• Proprietary technology to further remove minor impurities

Isosorbide esters; technical performance in PVC

Plasticising properties: plasticising efficiencies (Shore A&D)

Isosorbide esters

are primary

plasticisers

Required

properties can be

“tuned” by

changing the alkyl

chain

30

40

50

60

70

80

IsDH IsDHep IsDEH IsDO IsDiD DEHP

Shore A (70 phr)

Shore D (35 phr)

• Biobased flexible PVC makes only sense in combination with bio-plasticisers!

Typical synthesis

esterification from 180 ºC up to 250 ºC under Ar during 3-4 hrs

polycondensation in vacuo (P < 5 mbar) during 4 hrs

catalyst: Ti(OBu)4

Example:

isosorbide 2,3-butanediol succinic acid

O

O

OH

OH

H

H O

OH

O

OHOH

OH

O

O

O

O

H

H

O

O

OO

O

O

*

*

n

+ + - H2O

Ti (OBu)4

Isosorbide based powder coating resins

Noordover, B.A.J. , J. v. Haveren et al., Biomacromolecules 2006, 7, 3406-3416

0

10

20

30

40

50

60

70

50 60 70 80 90 100

isosorbide content [mol%]

Tg [

ºC]

Figure: The effect of incorporating different amounts of isosorbide on the Tg values of terpolyesters. ▲; 1,3–propanediol ●; neopentyl glycol ■; 2,3-butanediol.

Tg as a function of isosorbide content

Isosorbide based powder coating resins

Tri functional components (glycerol or citric acid) were included in

succinic acid- dianhydrohexitol polyester synthesis to induce

synthesis of OH or COOH functional terpolyesters

COOH

OH

HOOC

COOH

OH

OH

HO

• Glycerol (0.06 molar equivalent compared to succinic acid) incorporated

during synthesis polyesters at 230-250 ºC

• Citric acid (0.20 mol/eq); end capping of OH functional resins at 150 ºC

Isosorbide based powder coating resins

Isosorbide based powder coating resins Accelerated weathering

• Experiments carried out using high intensity Mercury lamp at high

temperature (~60 ºC) for 20 hours

• No change in film appearance:

- color

- gloss

• No cracking or other visible signs

of film deterioration

• IR measurements show strong

increase in –OH, -OOH and C=O

chain scission

• Reduced impact resistance (similar

to conventional systems)

• More pronounced yellowing of TPA-containing conventional systems

reference coating

weathered coating

Furan dicarboxylic acid could be a bio based alternative to terephthalic acid or (iso)phthalic acid)

Terephthalic acid used to produce e.g. PET (bottle, fleece) or e.g. Aramid fibres

Feedstocks for furans (C5, C6 sugars) are likely side streams 2nd generation bioethanol production

HOOC

O

COOH

2,5-FDACOOH

COOH

terephthalic acid

Furan building blocks: 2,5-FDA platform

PET wordt nu jaarlijks in miljoenen tonnen

geproduceerd uitgaande van aardolie

grondstoffen

Er is vanuit de industrie veel belangstelling voor

Biobased PET

Biobased PET

OMeOOC

OMeOOC

OH

O OHO

H

O

HOOH

HOOH

OH

D-fructose

Hemi-Cellulose

Me-2-furoate

HMF

HOOCO

COOH

OHOOC

OH

HMFA

(co)Polyesters OMeOOC

OH

O

OO

(co)Polyesters(co)Polyesters

Biosynergy

CCC

Biosynergy

DPI

Bioproduction

Bioproduction

Bioproduction

DPI

Furan building blocks: 2,5-FDA platform

Polybutylene 2,5-furanoate; 50 g scale melt polymerisation

2,5 FDA based polyesters

Polyesters have been described before, see e.g. Gandini et al, J. Polym. Sci, Part A, Polym.

Chem. 2009,47,295, but only at 1-3 gram scale

2,5 FDA based polyesters

Polybutylene 2,5-furanoate; 50 g scale

Results

Off-white brittle material after work-up

Mn 14,000 (1H-NMR end-groups, CDCl3/CF3COOD); DP = 70

Tg = 28 °C

Tc = 92 °C

Tm = 174 °C (lit. 163-165 °C )

+ HOOH O

O

O O

O**

O

OMe

O

MeO

O

CatalystAnti-oxidant

1) 180 C, N22) 220 C, N2

3) 240 C, 10 mbar

Polybutylene 2,5-furanoate; TGA (10°C/min, air)

PBT

PBF

Tm

Tm

2,5 FDA based polyesters

48

All polymers give colorless precipitates; Tm, Tg, Tc recorded

Colorless powders or transparent fibers

PEF PBT

PPF PBI

Mechanical properties will be determined

2,5 FDA Polymerisation trials

Biobased terephthalic acid

Wageningen technology:

Three step synthesis of aromatic di-acids from sugars

Step 1 > 90 % yields starting from commercial product at about

600 € tonne

Step 2 > 75 % yield

Step 3; currently approximately 50 % yield

Based upon approximately one year of research

Patent filing in progress

Overall yields are believed to be higher than GEVO’s approach

• biomass to ethanol

• ethanol to ethylene

• “biothene”

H

H

H

H

H

OH

H

H H

H

n

Braskem has started production polyethylene based on bioethanol:

Dow Chemicals previously announced production

Biobased polymers with identical structure

Technologies: Bioethanol

Pre-treatment required to make sugars available for fermentation

Technologies: Bioethanol

Example of enzymatic hydrolysis of lignocellulose

A,B,E Research targets

Improvement of product yields

Metabolic engineering towards higher butanol yields

Improvement of process economics

Alternative substrates for fermentation: Lignocellulosics (EOS-LT

Biobutanol), Seaweeds (EOS-LT project)

B-Basic Recycling (re-use of microbial biomass as nutrient, positive

effect)

High-cell density cultures, “in-situ” product removal

Buk Ack

A,B,E Approach

Butyrate

CO2

Glucose

Lactate Acetate Acetone

H2

Ethanol

CO2

Acetoin Butanol

pyruvate acetyl- CoA

butyryl- CoA

aceto-

acetyl- CoA

acetyl-P butyryl-P acetoacetate

EMP

Inhibition of acid production: No acetone production, Lower ATP yield

Fig.1 Simplified glucose metabolic pathway in C. acetobutylicum

I, B,E fermentation

Redirecting fermentation towards isopropanol; isopropanol is a

significant product as such and a precursor to biobased propylene

Results obtained

W W Y

Z

Glucose consumed [g/L] 34.30 61.99 69.26 67.79

Butyric acid [g/L] 0.21 2.02 1.08 1.06

Acetone [g/L] 0.17 5.70 0.35 0.09

Ethanol [g/L] 0.12 1.26 1.34 1.71

2-propanol [g/L] 4.47 0.10 7.27 8.37

Butanol [g/L] 8.08 8.98 11.80 12.95

Total solvent [g/L] 12.83 16.04 20.76 23.12

Culture time [h]* 33.5 49.5 29.9 28.0

Productivity [g/L/h] 0.41 0.41 0.69 0.81

Solvent yield [g solvents/g

subs.] 0.37 0.26 0.30 0.34

Isopropanol selectivity [g/g] 0.35 0.01 0.35 0.36

Acetone selectivity [g/g] 0.01 0.36 0.02 0.00

Table 1 : Wild type and transformants performance during fermentation on glucose (90g/L).

Isopropanol production doubled with regard to wild type wild type

Alternative substrates for fermentation

Laminaria digitata Ulva sp. (green) Alaria esculenta Palmaria palmata

Example: Seaweeds (EOS-LT Seaweed Biorefinery)

Characterization of materials: Biochemical analysis, pre-treatment hydrolysis, in collaboration with Pulp and Fibre Group

Characterization of hydrolysates (sugars, furfurals, organic acids, etc)

Toxicity and tolerance tests, fermentability

Develop a green

technology to

produce MeOH

from CO2 or CH4

Project for the production fo BioMeOH from CO2 is running (BioSolar program))

Biomethanoll

Styrenic and acrylic monomers

NH2

OH

O

OR

O

OH

O

J. Spekreijse, Dr. J. Le Nôtre

PCT International Application: “Olefin cross-metathesis applied to biomass”

Biomass Bio-ethanol

DDGS

Conversion of Protein Biomass into Styrene and Acrylates:

Separation PAL

Esterification

Protein Hydrolysis

Amino Acids

PAL Mixture

1) Esterification

2) Separation

OR

O

OR

O12.5 mol% catalyst

ethene (1 bar)

DCM, 40 oC, 24 h

+

J. Spekreijse, J. Le Nôtre

Cinnamates to Styrene and Acrylates by Ethenolysis Reactions:

Catalyst:

Hoveyda-Grubbs 2nd generation

R Conversion into products[a]

H 31%

Et 28%

n-Bu 39%

([a] ca. 15% of stilbene was formed)

0

5

10

15

20

25

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Ethene pressure (bar)

Co

nvers

ion

(%)

Cinnamic Acid

Ethyl Acrylate

0.02 M substrate, 5 mol% HG-2nd, DCM, 40 °C, 24 h

Pressure Screening:

Higher ethene pressure

leads to lower conversion

PCT International Application: “Olefin cross-metathesis applied to biomass”

(0.05 M, R = H, Et, n-Bu)

Co-production of bulk chemicals based upon biomass

Other acrylic monomers potentially can be

co-produced from carbohydrate based resources

Novel resources

Conclusions

Both flexible as well as rigid “aromatic” building blocks

can be created based upon renewables

These building blocks can be used for the creation of

novel thermoplastic or thermoset materials, or

Can serve as drop in solutions (e.g. propylene, styrene,

acrylates)

Economical perspectives of future biorefineries can be

optimised by focusing on bulk chemical production

Preferably usage should be made of waste streams/crops

not interfering with food production

The ambition for the future…

Energy

Bulk chemicals

Fine/

Pharmaceuticals

Sustainable

Catalytic

Processes

Biomass

and

wastes

Recycling

CO2

Source: CATCHBIO project