Processing Swedish lignocellulosic residual material to furan pre-cursors "Furu2Furan" - Dennis Jones, Bror Sundqvist Sune Wännström
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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 DevelopmentFuru2Furan Consortium comprising whole value chains Companies members of EcoBuild Competence Center (Competence centre for eco-efficient and innovative wood-based materials)
SP – A uniting hub in
Bioeconomy
Vision
SP shall be a uniting force and BIO-
a central resource contributing
with knowledge, research ECONOMY SP PROCESS
DEVELOPMENT
resources and management,
test facilities and coordination
of bioeconomy initiatives in
SwedenWhy are we doing this? 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
The biorefinery concept Jan van Dam, COST FP1205 presentation 2013
The biorefinery concept – Furu2Furan
High value
chemicals
Jan van Dam, COST FP1205 presentation 2013Furu2Furan concept
Softwoods yield hexoses
Hardwoods and agri-fibres yield pentoses
Some pathways
Conversion of HMF
2-hydroxymethylfuran 2,5-Dimethylfuran
2,5-Furandicarboxylic acid
Platform chemical Bio-fuel
Monomer for polymer
production
Methylfuran 5-hydroxymethylfurfural 2,5-Dimethyltetrahydrofuran
Bio-fuel (HMF) Solvent
2,5-bis(hydroxymethyl)furan Levulinic acid Formic acid
Monomer for polymer Bulk chemical Bulk chemical
productionHigh-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 productsPossible high-value bulk chemicals from the F2F project
Maleic anhydride (currently 100% fossil based) Thermoset polyesters
- Global production: worth 550 million Euro & polymerisat. catalyst
Adipic acid (currently 100% fossil based) Polyamide (Nylon)
Global annual production: 2.3 million ton
Worth: 845 million Euro
Caprolactone (currently 100% fossil based e.g. Shoe soles,
Perstorp production (largest producer globally): 12 kton/year? Medical plastics
Perstorp caprolactone sales worth 60 million Euro/year
Polymer building block
Hexane diol (currently 100% fossil based)
for e.g. PUR and PE
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)
)Starting materials
A. Under-utilized forest products streams
Saw dust
Residuals from forest harvesting (stubs, tops and branches)
Prehydrolysate from dissolving pulp production
TMP and CTMP process waterStarting materials
B. Under-utilized agricultural byproduct streams
Wheat straw
Wheat bran
Straw and bran from other Lantmännen cropsLab scale work: SP-PD Chemical Processes: Xylose
to Furfural
Furfural
From Hemicellulose
Furfuryl alcohol
Furfural: Extracted from hydrolysate or transformed from isolated sugar
Industrial production in China, South Africa, Dominican republicLit 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 Microwave
mL) run under mild conditions. reactor
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
RP-HPLC
Analysis of furfural yield by HPLC and/or
LCMSResults- 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…
Filtration:Processum Pilot Park - Örnsköldsvik
•Liquid-liquid extraction
•Filter press
•Reactor system for synthesis
•Spinning unitResults 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 phaseLiterature 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 glucoseExperimental 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 trialsOutline 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 intervalsScreening 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.Polymer (Humins)
formation
Reaction phases
HMF +
hydrated HMF +
HMF glucose
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
* 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 Catal
yst
• Decreases HMF degradation and
polymerization
*More humins with scale up in 20 ml
microwave vial
Alternative to agitation in larger scale
processing could be sonicationSolvent type
Extraction solvent is important
• Extracts HMF from water
M-THF: 8% HMF yield from glucose
MIBK: 27%
Catal
2-butanol: 30%, and 2% less HMF in water phase yst
2-butanol gave best results, but similar to MIBK
or Glucose
Is MIBK better for continuous processing?
-2-butanol dissolves a large amount of
waterConcentration 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 HMFScaling up: Pretreatment reactor
•Built for 230 °C and 30 bar
•Heated by steam (22bar)
•Used for batch reactionsBoth Mild and Harsh systems for wheat straw scaled
up in the Demo-Plant
Demo Run Plan
Target: collecting 100 litres of xylose rich
hydrolysate and 100 litres of furfural rich
hydrolysate after dilute acid hydrolysis of
wheat straw.
Test Production Temperature Acid Residence Sampling
time Load time
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 100Biorefinery Demo Plant
Demo plant Domsjö Biorefinery site
Demo Plant Facts
Fully integrated process from feedstock to distilled
product
Operated 24h/ 7d
Two continuous flow-through hydrothermal reactors
One or two step acid hydrolysis
Dilute acid pretreatment + enzymatic hydrolysis
Five 10 m3 bio-reactors
Enzymatic hydrolysis
Fermentation
Cultivation
GMM certified
Flexible
Process configurations
Forest and agro feedstocks
Biorefinery applications (sugar platform)
Capacity, 2 tons of dry wood chips / 24 hLayout
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 EquipmentHydrothermal Pre-treatment of Lignocellulose
Feedstock
Feed
wood
stock
chips
screw-s
impregnation
tank
horizontal reactor
steam
screw-s
1 H2SO4
screw-s
steam
vertical
reactor
filtrate
sample position
slurry
tankEarlier 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
Fermentation
& distillation
Ethanol
less Enzymatic
hydrolysed treatment Chemical HMF
Processes Furfuryl alcohol
Cellulose Dimethylfuran (fuel)
Pretreatment
&
fractionation Sugars
Ligno-cellulosic Sugars
Biomass (sawdust) and Fraction- Furfural
ation Chemical Furfuryl alcohol
furans Processes FA/Furfural-mix
C5 & C6
(oligo-
& poly- Or further hydrolysis
sacharides) to furans
Lignin-rich solid residue
Pellet
processsing
EnergyDiscussion 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 scale Pilot scale Up to 10 ml Potential up to 0.6 m3
Glucose/Fructose to HMF and downstream
OH
OH O
H3 C O
OH O
HO
OH
Fructose HMF
From Cellulose
OH
O
H3C O OH
OH O
HO
OH
HMF
Fructose
Fructose is more reactive and selective to make HMF
than glucose i.e. higher yield
Dimethyl furan
Starting from glucose likely involves isomerization to FDCA
fructose before dehydration to HMF
& Other Chemicals
2,5-bishydroxymethyl furanConclusions 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)You can also read
