Processing Swedish lignocellulosic

residual material to furan pre-cursors

“Furu2Furan”

Dennis Jones, Bror Sundqvist

SP Wood Technology / EcoBuild

Sune Wännström

SP Energy Technology

William Mackintosh, Johan Malmberg, Anna Stenemyr

SP Process Development

Furu2FuranConsortium comprising whole value chainsCompanies members of EcoBuild Competence Center(Competence centre for eco-efficient and innovative wood-based materials)

VisionSP shall be a uniting force and a central resource contributingwith knowledge, research resources and management, test facilities and coordinationof bioeconomy initiatives in Sweden

SP – A uniting hub in

Bioeconomy

SP PROCESS

DEVELOPMENT

BIO-

ECONOMY

� Today: too much focus on biofuel production (which may

not be the optimal use of the whole biomass)

� The furanic route to platform chemicals and high-value

commodities is almost neglected in current biorefinery

development

� There are some potential “winners” for the future biobased

economy but need to secure that enough chemicals for

these is produced in future biorefineries

Why are we doing this?

The biorefinery concept

Jan van Dam, COST FP1205 presentation 2013

The biorefinery concept – Furu2Furan

High value

chemicals

Jan van Dam, COST FP1205 presentation 2013

Furu2Furan concept

Softwoods yield hexoses

Hardwoods and agri-fibres yield pentoses

Some pathways

5-hydroxymethylfurfural

(HMF)

Methylfuran

Bio-fuel

2-hydroxymethylfuran

Platform chemical

2,5-Dimethylfuran

Bio-fuel

2,5-bis(hydroxymethyl)furan

Monomer for polymer

production

Levulinic acid

Bulk chemical

Formic acid

Bulk chemical

2,5-Dimethyltetrahydrofuran

Solvent

2,5-Furandicarboxylic acid

Monomer for polymer

production

Conversion of HMF

High-value end products of the F2F project

� Furfurylated wood (Kebony) with aesthetic appearance and performance similar to durable tropical timbers (and preservative treated timbers)

- European market for durable hardwood (tropical timber):

6 million m³/year => value: 6 billion Euro

- European market for preservative treated wood:

6 million m³/year => value: 1.5 billion Euro

� Coil Coatings (currently 99.9% fossil resource based). BioCoilCoat aims at 60% biobased.

SSAB alone use 4 kton/year (?): worth 20 million Euro

European market: 100 kton/year (?): worth 550 million Euro

� Thermoset composites today 99% fossil based

European market: 10 billion Euro worth?

bioderived resins can replace fossil based resins for many products

Possible high-value bulk chemicals from the F2F project

� Maleic anhydride (currently 100% fossil based)

- Global production: worth 550 million Euro

� Adipic acid (currently 100% fossil based)

Global annual production: 2.3 million ton

Worth: 845 million Euro

� Caprolactone (currently 100% fossil based

Perstorp production (largest producer globally): 12 kton/year?

Perstorp caprolactone sales worth 60 million Euro/year

� Hexane diol (currently 100% fossil based)

BASF production (largest producer globally): 50 kton/year

Worth: 310 million Euro

� Aviation fuel (currently 100% fossil based). Possibly DMFu

Global annual prod of Jet fuel: 5 million barrels worth 500 million Euro

� Green aromatic solvents

Global prod. of BTX: 87 Mton worth 91 billion Euro

(BTX means Benzene, Toluene, Xylenes)( )

Thermoset polyesters

& polymerisat. catalyst

Polyamide (Nylon)

e.g. Shoe soles,

Medical plastics

Polymer building block

for e.g. PUR and PE

� Saw dust

� Residuals from forest harvesting (stubs, tops and branches)

� Prehydrolysate from dissolving pulp production

� TMP and CTMP process water

Starting materialsA. Under-utilized forest products streams

� Wheat straw

� Wheat bran

� Straw and bran from other Lantmännen crops

Starting materialsB. Under-utilized agricultural byproduct streams

Lab scale work: SP-PD Chemical Processes: Xylose

to Furfural

From Hemicellulose

Furfural

Furfuryl alcohol

Furfural: Extracted from hydrolysate or transformed from isolated sugarIndustrial production in China, South Africa, Dominican republic

Lit review from C5, xylose and furfural

Showed that furfural is currently being produced commercially from bagasse and/or corn stover

Inexpensive, high yields, tuned catalysts and conditions

However not from wheat straw.

Patents and publications containing furfural and wheat straw

Conclusions from literature

• More severe conditions, time, temp, acid: more furfural

• Milder conditions: more xylose to then produce furfural in a 2nd step.

Experimental

Step 1:

Wheat straw and dilute sulfuric acid added to a microwave vial (10-20 mL) run under mild conditions.

The slurry was filtered, the filtrate analyzed, then used in step 2.

Step 2:

Filtrate & methyl isobutyl ketone (MIBK) combined in microwave vial (2-5 mL) High temps and short reaction time

Analysis of furfural yield by HPLC and/or LCMS

Microwavereactor

RP-HPLC

Results- mild prehydrolysis of wheat

straw on the lab scale

Step 1: From mild conditions: A range of results is

observed in furfural and xylose content

The filtrate was then further reacted in step 2…

•Liquid-liquid extraction

•Filter press

•Reactor system for synthesis

•Spinning unit

Filtration:Processum Pilot Park - Örnsköldsvik

Results step 2-Conversion of xylose to

furfural

Higher temperatures: Highest yields of furfural were

achieved from the mildest hydrolysis runs from step 1.

72% yield obtained (78% in total, Aq phase included)

Yield in organic phase

Literature Study of C6 sugars to HMF

Glucose is a sugar from cellulose and hemicellulose

Similar to mannose found in hemicellulose

Fructose to HMF

Vast amount of information in literature- 8 k items in scifinder.

Little in terms of

• Scaling up and production processes

Many catalysts for fructose to HMF

Not much reported regarding glucose to HMF

Fewer catalysts to convert glucose to HMF

Lower yields from glucose

Experimental Work Flow for C6 sugars

Conditions and catalysts screened on

a small scale

• Via microwave in 2-5 ml vials

• Analysis of HMF performed by

HPLC and/or LCMS

Reaction of fructose to HMF first

investigated

• Higher yields and much

broader range of possibilities

• Catalysts screened

Then glucose to HMF investigated

• With use of knowledge

obtained from fructose trials

Outline of the Experimental Parameters Considered

Catalyst

Soluble or insoluble

Reaction phase

biphasic (both water and solvent) vs. single phase

Ratio of water to solvent in biphasic system

Aqueous Phase Ionic Strength

Agitation

Solvent type

Concentration of sugar in the water phase

Temperature

Time

Replacing the solvent at intervals

Screening of Catalysts

Less than desirable yields from:

Zeolites, Ag and Cs based polyacids,

phosphorylated niobium oxide, sulphuric acid

2 Best performers with fructose:

Phosphorylated Tantalum hydroxide vs. Calcium

phosphate (CaP2O6)

Next in trials with glucose:

Only 20% yield compared to 27% yield w same

conditions

• Glucose to HMF, 190oC, 20 min, 3 ml

MIBK to 2 ml H2O

*Daorattanachai, P. et al. Conversion of fructose, glucose, and cellulose to 5-hydroxymethylfurfural

by alkaline earth phosphate catalysts in hot compressed water, Carbohydrate Research, 363 (2012) 58-61.

* Yang, F. et al. Tantalum compounds as heterogeneous catalysts for saccharide dehydration to 5-hydroxymethylfurfural.

Chemical Communications, 47 (2011) 4469-4471.

Reaction phases

Biphasic gave the best yields, with the solvent extracting HMF

Inhibits degrading/polymerizing of HMF in the water phase as it is extracted

Ratio of solvent to water likely requires optimization depending on the system

solvent:H2O optimum at 3:2 or 4:1

Higher concentrations of sugar in water does create more insoluble hummins and side reactions

Polymer (Humins)

formation

HMF +

glucose

HMF +

hydrated

HMF

* Rasmussen, H. et al. Formation of degradation compounds from lignocellulosic biomass in the

biorefinery:

Sugar reaction mechanisms, Carbohydrate Research, 385 (2014) 45-57.

Agitation

Agitation is very important

• Creates maximum contact between the 2

phases.

• Important to transfer HMF from the

aqueous phase

• Decreases HMF degradation and

polymerization

*More humins with scale up in 20 ml

microwave vial

Alternative to agitation in larger scale

processing could be sonication

Catal

yst

Solvent type

Extraction solvent is important

• Extracts HMF from water

M-THF: 8% HMF yield from glucose

MIBK: 27%

2-butanol: 30%, and 2% less HMF in water phase

2-butanol gave best results, but similar to MIBK

Is MIBK better for continuous processing?

-2-butanol dissolves a large amount of

water

Catal

yst

or Glucose

Concentration of Sugar in the Aqueous Phase

The higher the concentration, the lower the yield

Due to HMF coming in contact with glucose and itself to form humins

This will also require optimization depending on the system

30 wt% glucose in water creates a large amount of side products

• Determined by HPLC

• Also much lower yields

6 wt% glucose in water used in most trials to provide high yields of HMF

Scaling up: Pretreatment reactor

•Built for 230 °C and 30 bar

•Heated by steam (22bar)

•Used for batch reactions

Both Mild and Harsh systems for wheat straw scaled

up in the Demo-Plant

Test Production

time

Temperature Acid

Load

Residence

time

Sampling

Unit h C % min Litres

1 6 187 0,2 5 1

2 6 190 0,5 5 1

4 6 205 1 5 1

5 6 215 1 5 1

5 12 187-190 0,2-0,5 5 100

6 12 205-215 1-1,5 5 100

Target: collecting 100 litres of xylose rich hydrolysate and 100 litres of furfural rich hydrolysate after dilute acid hydrolysis of wheat straw.

Demo Run Plan

Biorefinery Demo Plant

Demo plant

Domsjö Biorefinery site

Fully integrated process from feedstock to distilled product

Operated 24h/ 7dTwo continuous flow-through hydrothermal reactors

One or two step acid hydrolysisDilute acid pretreatment + enzymatic hydrolysis

Five 10 m3 bio-reactorsEnzymatic hydrolysisFermentationCultivationGMM certified

FlexibleProcess configurationsForest and agro feedstocksBiorefinery applications (sugar platform)

Capacity, 2 tons of dry wood chips / 24 h

Demo Plant Facts

1. Raw material intake

2. Feeding vessel

3. Steaming and impregnation

4. Pretreatment

5. Neutralisation and inhibitor control

6. Enzymatic hydrolysis and fermentation

7. Yeast propagation

8. Distillation

9. Product tank

10. Filter press

11. Solid material to incineration

12. Liquid to incineration/ biogas production

13. Evaporation Equipment

Layout

horizontal reactor

vertical

reactor

impregnation

tank

slurry

tank

screw-s

screw-s

screw-s

H2SO

41

steam

steam

filtrate

sample position

wood

chips

Hydrothermal Pre-treatment of Lignocellulose

Feedstock

Feed

stock

Earlier experiences (not targeting high yield of

furans)

Wheat straw

Mild pretreatment; ~2-6 g/l furfural, ~0-1 g/l HMF.

Harsh preteratment >10g/l

Spruce chips

Mild - medium pretreatment; ~2g/l furfural, ~3 g/l HMF

Pine chips

Medium – harsh pretreatment; ~4 g/l furfural, ~8-10 g/l HMF.

Process – Sawdust and Wheat Straw

Ligno-cellulosic

Biomass (sawdust)

Pretreatment

&

fractionation

Lignin-rich solid residue

Sugars

and

furans

less

hydrolysed

Cellulose

Enzymatic

treatment

Pellet

processsing

Chemical

Processes

Chemical

Processes

Energy

Furfural

Furfuryl alcohol

FA/Furfural-mix

Fraction-

ation

HMF

Furfuryl alcohol

Dimethylfuran (fuel)

C5 & C6

(oligo-

& poly-

sacharides)

Fermentation

& distillationEthanol

Sugars

Or further hydrolysis

to furans

Discussion

Understanding of the different streams. Contents, Assays, purity,

analytical methods and control.

Control of hydrolysis and extraction of Furans (Pilot/Demo plant)

How to process the different streams before chemical processing if

needed. Filtration, extraction, other methods

Defining Target furans of value based on the different streams and

demand.

No industrial process available for HMF from lignocellulose

Separation Development

Feed stream: Sawdust hydrolysate containing furans, excluding lignin (from Örnsköldsvik).

Membrane filtration to separate furans from hydrolysate

Laboratory tests either at SPPD or at Alfa Laval

Pilot scale tests at Örnsköldsvik

“Purified streams” used for downstream chemistry

Extraction to separate furans from hydrolysate

Investigate downstream separation of product streams (when applicable)

Reason for using filtration technology

Less chemicals in aqueous streams

Greater ease of disposal

Less need for additional chemical adidtional for clean up

Typically a TMP mill will release approx 3-5kg carbohydrates per

m3 of water

This means approx 300-400 kg of carbohydrates per hour

Potentially 3500 tonnes per annum ”lost”

Potential of processing

Concept of process

Plant design

Microwave applications

Lab scaleUp to 10 ml

Pilot scalePotential up to 0.6 m3

Glucose/Fructose to HMF and downstream

Fructose is more reactive and selective to make HMF

than glucose i.e. higher yield

Starting from glucose likely involves isomerization to

fructose before dehydration to HMF

O

OHO

HMF

O OHH3C

OHHO

OH

Fructose

O

OHO

HMF

O OHH3C

OHHO

OH

Fructose

From Cellulose

FDCADimethyl furan

2,5-bishydroxymethyl furan

& Other Chemicals

Conclusions of Furu2Furan

• Literature review, lab based experiments, pilot scale experiments

and demo plant runs carried

• All in a period of 9 months

• Additional work

• Environmental aspects

• Financial aspects

• Logistics

• Devising alternative pathways to new chemical derivatives

• Investigating pilot scale microwave processing

• Strong links built between industry partners

• New projects underway (OptiFuran, Furan2Market)