Chemicals driven biorefinery

research

Dr. Jacco van Haveren

Programme manager Biobased

Chemicals and Fuels

Wageningen UR/Food and

Biobased Research

From Biomass to Bioproducts;

Trends in Science and technology

May 14th, 2013

Biobased Products @ Food & Biobased Research

Leading research group in the Netherlands

80+ fte,

Confidential bilateral projects with multinationals, SMEs

Public-private sponsored projects

BU comprises three interconnected Programmes:

Biorefinery

Biobased Chemicals & Fuels

Biobased Materials

Close link with Food Technology Centre

Atmospheric

Distillation

High

Vacuum

Distillation

Hydrotreating

Isomerisation

Catalytic

Reforming

Alkylation

Polymerisation

HDS

Hydro-

desulphurisation

HDS

Catalytic

Cracking

Hydrocracking

Lube Oil

Plant

Therm. Crack./

Visbreaking

Coking

Hydroconversion

PRIMARY

SEPARATION

CONVERSION REMOVAL OF

IMPURITIES

LIGHT ENDS

UPGRADING

NAPHTHA

GASOLINE

LPG

CRUDE

OIL

KEROSINE

GAS OIL

LUBE OIL

FUEL OIL

BITUMEN

Vacuum

Residue

Propane/Butane

Vacuum

Distillates

Light gasoline

Naphtha

Kerosine

Gas oil

Atmospheric

Residue

Butane

Cracked gasoline

Atmospheric

Distillation

High

Vacuum

Distillation

Hydrotreating

Isomerisation

Catalytic

Reforming

Alkylation

Polymerisation

HDS

Hydro-

desulphurisation

HDS

Catalytic

Cracking

Hydrocracking

Lube Oil

Plant

Therm. Crack./

Visbreaking

Coking

Hydroconversion

PRIMARY

SEPARATION

CONVERSION REMOVAL OF

IMPURITIES

LIGHT ENDS

UPGRADING

NAPHTHA

GASOLINE

LPG

CRUDE

OIL

KEROSINE

GAS OIL

LUBE OIL

FUEL OIL

BITUMEN

Vacuum

Residue

Propane/Butane

Vacuum

Distillates

Light gasoline

Naphtha

Kerosine

Gas oil

Atmospheric

Residue

Butane

Cracked gasoline

Crude oil is refined into a slate of products

Courtesy: ECN

Alternative sources of energy

wind

hydropower Nuclear

energy

Solar energy

biomass

Biorefinery Existing and future biorefineries will refine biomass into a

spectrum of products

Total Crop Yields

Wet Weight and Dry Weight Yields

0

10

20

30

40

50

60

70

80

90

100

Cas

sava

Gra

ss

Luce

rne

Mai

ze

Oil pa

lm

Pot

ato

Rap

esee

d

Sor

ghum

Soy

a be

an

Sug

ar b

eet

Sug

ar c

ane

Sun

flower

Switc

hgra

ss

Tobac

co

Whe

at

Willo

w tr

ee

ton

/ha

Wet Weight

Dry Weight

143 140 240

Total Biomass Production

Best Practice Yields

Above 10ton/ha/a dry weight = Good

Above 20ton/ha/a dry weight = Great

Above 30ton/ha/a dry weight = Fantastic

Source : Johan Sanders

Food and Biobased research in Biorefinery

Pretreatment &

Extraction

New biomass

Byproducts

Crops

Lignocellulose

Fresh biomass

Aquatic biomass

Residues

Traditional crops

Feed & Food

Materials

Chemicals

Energy & Fuels

Biomass chain aspects: availability, quality, sustainability, logistics

Oils & fats

Sugars

Fibres

Proteins

(Bio

)chem

ical

Convers

ion

Biomass chain design and policy advise

Biobased Chemicals

Products from existing biorefineries

Isohexides (1,6;3,6-

dianhydrohexitols)

Isohexides Isosorbide and other isohexides from edible biomass

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

Isosorbide based powder coatings

Powder coatings; solventless coatings electrostatically applied to mostly

metal surfaces

Isosorbide based powder coating resins

95-100 % biobased resins and coatings with required properties can

be obtained

Isoidide more reactive than

Isosorbide in resin synthesis

Films are impact and solvent resistant

A decreased yellowing compared to

TPA-containing conventional systems!

reference coating

weathered coating

Isosorbide based powder coatings

Isoidide

Powder coating results indicated an enhanced reactivity of isoidide in

polymer synthesis

Iditol and isoidide; rare hexitols/isohexides

EP1647540, US 7674381 to Roquette Frères:

Convenient method for preparation of L-iditol, but not for isoidide

14

Results:

- Epimerisation of isosorbide into isoidide is effected by Ru/C is a

catalyst

- Thermodynamic equilibrium (56 % of isoidide) is reached after a few

hours of reaction

- Isohexides can be separated by distillation

- Same equilibrium mixture reached starting from isomannide

Ongoing:

- Incorporation of isoidide into polyesters ongoing

- Patent filing

O

O

OH

OH

H

H

O

O

OH

O

H

H

O

O

OH

OHH

H

O

O

OH

OH

H

H

O

O

O

OH

H

H

+ H2

- H2

- H2

+ H2

- H2

+ H2

+ H2

- H2

Isosorbide IsomannideIsoidide

Likely mechanism

Improved Methods for the Synthesis of Isoidide

Products from alternative biomass sources

Lignocellulosic biomass

Agricultural residues

Aquatic biomass

Strategy pretreatment development

Product-driven pretreatment and fractionation

Retain intrinsic functionality of components as much as possible

Integrate pretreatment with further downstream processes (e.g. separation, fermentation, chemo-catalysis)

Use insight in biomass* composition and supply chain

*lignocellulose, fresh biomass, algae, agicultural residues

Use technology know-how as input for developing sustainable value chains and vice versa

Source; Rob Bakker, Paulien Harmsen

Focus areas for pretreatment R&D

Mild pretreatment

Selective extraction of lignin, C5 sugars, polyols, proteins, starch

Reduce water holding capacity of biomass

Process integration, reduce costs

Valorise all streams!

Gain more fundamental insights in pretreatment process in close collaboration with academic partners

Source; M.v. Gool; Wageningen

University, 2012

Pretreatment worldwide (~40 pilot plants)

Steam explosion (Abengoa, Andritz, QUT)

Acid (Sekab, Petrobras, Verenium)

Organosolv (Lignol, Chempolis)

Liquid hot water (Inbicon)

Concentrated acid (Weyland, BEL)

Lime and oxygen (Terrabon)

AFEX

ASSF

Consolidated bioprocessing (Mascoma)

StroStro

Source; Rob Bakker, Paulien Harmsen

Straw to fermentable sugars, lignin

Wheat straw

Pretreatment Enzymatic hydrolysis

Fermentation

Lignin

Ethanol

Polymeric sugars

Monomeric sugars

Fractionation efficiency Delignification up to 70 - 80% Improvement of enzymatic degradability

Extrusion

Enzymatic hydrolysis Conversion of glucan and xylan to monomeric sugars, with low fermentation

inhibitors

Lactic acid

Source; Rob Bakker, Paulien Harmsen

Empty Fruit Bunch (EFB)

Abundant and cheap lignocellulosic biomass

Worldwide production approx. 20 Mton DM/y

Collected at palm oil mills

Reasonably high in cellulose

Very limited applications so far

Bulky and wet (dry matter <35 wt%)

Inefficient as fuel due to low calorific value

Returned to plantation sites as compost

Shredded fibres in matrasses

FFB EFB

Source; Rob Bakker, Paulien Harmsen

Composition of fresh EFB

Aim; developing process for dissolving cellulose

Cellulose with high cellulose content (>90%) and high, uniform molecular weight distribution

Price 1600-2000 €/ton*

Estimated market volume 4.5 Mton/y*

Raw material for cellulose-derived products like textiles (viscose, rayon), cellulose derivatives (CMC) and bioplastics (cellophane)*

Current situation

Wood and cotton as raw material

Large scale processes (400 kton/y, kraft and sulfite)

*Source: Keijsers et al., The cellulose resource matrix, Carbohydrate Polymers, 2013

Biorefinery concept

Parameter Dissolving pulp specifications

Degree of polymerisation (DP) >1000

Kappa nr (delignification) 1

Hemicellulose content <5%

α-Cellulose content (=undegraded cellulose) >90%

Source; Rob Bakker, Paulien Harmsen

Project results

Proof of concept demonstrated

Patent application filed

(Harmsen et al. WO2011/126369A1)

Project funded by Biority BV and subsidized by the Dutch government

Pilot-scale in Malaysia is in progress

Process gives next to dissolving cellulose also access to high quality lignin

Lignin research

Lignin is found in plants and

trees and is a rest stream from:

1. Established Pulp and Paper industry

(50 M t/y, 1 M t/y products)

2. Novel Biorefinery industry (>20 M t/y)

Major aromatic resource in Biobased

Economy

Complicated aromatic structure

Complexity and heterogeneity has

limited its use in materials and for

chemicals production

(softwood lignin structure Brunow 2001)

25

OMe

HO

OH

OH

OMe

O

HO

HO

O

MeO

H O

HOOMe

O

HO

OMe

OHO

OH

O

MeO

O

MeO

OH

O

OH

OMe

O

HO OMe

HO OH

HO

HO

HO

OMeO

OH

OH

O

OHO

HO OMe

MeO

OH

O

OH

OMe

HO

O

HO

HO

OMeO

OH

OH

O

OHO

O OMe

MeO

OH

O

OH

OHHO

OMeO

OH

OH

O OMe

OH

O

MeO

H O

O

HO

MeO

O

O

OH

OMe

L ignin

OMe

OHOOMe

OHO

HO

Lignin

Source: Richard Gosselink

Lignin research @ WUR-FBR

O

HO

HO

OMeO

OH

OH

O

OHO

O OMe

MeO

OH

O

OH

OHHO

OMeO

OH

OH

O OMe

OH

O

MeO

HO

O

HO

MeO

O

O

OH

OMe

Lignin

OMe

OHOOMe

OHO

HO

Lignin

Binders/resins

Ocobinders

Ocobinders

Polymerisation Depolymerisation

Composites

Coatings

Surfactants

Chemicals

Chemical/ Enzymatic upgrading

(Bio-)catalysis

Source: Richard Gosselink

Lignin performance products

Application development at WUR-FBR

lignin as binder

plywood / fibre boards

lignin as (bio)polymer additive

U.V. stabiliser & colouring agent

lignin based coatings

lignin derivatives as wood preservative

lignin as surfactant, emulsifier

lignin depolymerisation chemicals

Source: Richard Gosselink

Catalytic lignin depolymerisation

RT: 4.00 - 23.00

4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Re

lative

Ab

un

da

nce

10.84

12.02 20.4214.68

15.2913.048.54 8.62 16.09 20.37

14.0311.17 16.27 22.3212.59 19.108.84 17.804.04 19.199.90 20.4713.297.224.38 21.005.81 7.277.08

NL:7.59E6

TIC MS Lignin160311

Up to 20 % of lignin converted into fraction with more than 50% of one

specific phenol!

Non-supercritical conditions

Source; Daan van Es, Frits v.d. Klis

Biorefining of sugarbeet pulp

Within EU annually approximately 25-30.106 tonnes of sugarbeet pulp (SBP) are being produced

SBP is a byproduct of sugar refining (agricultural residue)

Cosun produces annually about 1 million tonnes of SBP (25% dry matter)

SBP contains a mixture of components not suitable as human food

Cosun is interested in valorising SBP towards non–food applications

Cosun teams up with Wageningen UR/FBR and other partners in

valorising SBP

Picture sugarbeet (source Cosun)

Biorefining of sugar beet pulp

Number of projects awarded within Topsector Agri&Food

Overall aims of the projects

Continue developing biorefinery process for isolating monomeric sugars

from sugarbeet pulp

Develop new catalytic technologies to produce high purity building

blocks for high performance polymers based on sugarbeet pulp as raw

material

Develop new chemical technologies to produce these high performance

polymers

Investigate the properties of these new materials, and compare to

conventional materials

Obtain insight into the technical and economical viability of these new

bio-based polymers

30

Second generation 2,5 FDCA based upon SBP

Key; catalytic oxidation of pectin sugars

Mild conditions (room temperature)

High conversions (>99%)

High selectivity (>97%)

Short reaction times (<3h)

Environmentally benign:

Air can be used for the oxidation

Patent filed:

● Catalytic oxidation of uronic acids to aldaric acids

● Subsequent conversion aldaric acid into 2,5 FDCA

31

32

FDCA based polyesters

Polymerisation of 2,5-FDCA

Successful melt-polymerisation (various diols)

Low coloured materials obtained

Post condensation developed for PEF:

Mw ranging from 6,000 up to 170,000 g.mol-1

(Bottle to fibre grade materials!)

Aquatic biomass: Wageningen UR micro-algal

research

Maximizing productivity/yield

Reduction of energy input

Control/design of products

Biorefinery

Scale up

Design scenario’s

Source: Maria Barbosa, Gerrit Eggink

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; aquatic biomass

Source: Rolf Blaauw

Production of alkyd paints for decorative paints

Extraction of pellets from Delfzijl (30-6-2010) open pond system

600 gram pellets were extracted with hexane using a Soxhlet apparatus

About 19-20% (w/w) lipid/oil fraction was extracted

Fatty acid profile dependent on time of harvesting the microalgae

Source: Rolf Blaauw

FBR; huge knowledge on biobased chemicals

37

In case of further questions

Please contact our NOST offices abroad directly,

or through the central office:

● internet: www.IAnetwerk.nl

● telephone: + 31 88 602 8237

● e-mail: ianetwerk@agentschapnl.nl

or contact this speaker directly:

● internet: www.wageningenur.nl/fbr

● telephone: +31-317-480179

● e-mail: jacco.vanhaveren@wur.nl