1

Dmitry Yu. MurzinÅb Ak d i U i it

Catalytic transformations of woody biomass

Åbo Akademi University

Turku, Finland

1640

Wood

DP=10 000

DP=100-300

Part of lignin structure

2

It is misleading (although often done) to describe reactions of some model

Methodology: feedstock

compounds, which are petroleum derived and supplied from commercial suppliers, and refer to them as “biomass derived” even if in principle they could be derived from biomass.

The analytical procedures reported in the lit t ti i l t

Methodology: analytics

literature sometimes are very incomplete, because of the objectives of a particular study and available resources in terms of instruments, time, costs and human skills.

3

It is worth mentioning that in many papers i th j l ith hi h i t

Methodology: mass transfer

even in the journals with a high impact factor, size of catalysts grains is not even mentioned, thus influence of internal diffusion remains obscure. External diffusion limitations can also playExternal diffusion limitations can also play a role.

Characterization of catalysts and their f ti h ld b f bl

Methodology: characterization

surface properties should be preferably done in–situ or in conditions relevant to catalysis, since surface properties can depend on the pH of the solution, presence of surfactants, type of solvent, and ionic strength of the solution.

4

• Separation of the components of li ll l i bi i f f b i

Methodology: separation

lignocellulosic biomass is far from being trivial and should be done with selective extraction.

• Each fraction should be treated in a specific ways: cellulose, lignin,specific ways: cellulose, lignin, hemicelluloses and extractives using catalysis (homogeneous, heterogeneous and enzymatic)

Products separation can be a bottleneck, since conventional methods of separations

Methodology: separation

since conventional methods of separations used in chemical and petrochemical industry (e.g. distillation) cannot be readily applied in many instances, therefore such methods as preparative chromatography, nanofiltration, ion-exchange, etc, should be utilized.

5

• Structure sensitivity

Methodology: kinetics

• Size of molecules• Conformational analysis

• More knowledge on the specific catalysis for transformation of lignocellulosic

Methodology: catalysis

for transformation of lignocellulosicbiomass is urgently needed

• Deactivation of traditional heterogeneous catalysts used in biomass processing is a very serious issuey

6

Biorefinery

Sugar Pl tf

Sugar Feedstocks & Lignin Residues

Thermo-Chemical Platform

Platform

Biomass

Fuels, Chemicals, Materials, Heat & Power

Mixed Sugars

CO, H2, Bio-oils

“The Integrated Biorefinery”

Syngas, Pyrolysis-oils

Pyrolysis

7

BiomassPyrolysis

Gases

Pyrolysis of biomass

Pyrolysiswithout O2

400-600°C

Gases Condensation

Char Bio OilAtte Aho

GasCO, CO2, H2 and hydrocarbons

Pyrolysis products

Bio OilLiquid phase, containing acids, esters alcohols, aldehydes, ketones, phenols …

CharCharSolid phase, a complex carbon matrix

A. Aho, N. Kumar, K. Eränen, T. Salmi, M. Hupa, D. Yu. Murzin, Catalytic pyrolysis of woody biomass in a fluidized bed reactor: influence of the zeolite structure, Fuel, 2008, 87, 2493

8

• Carbohydrates, cellulose and hemicellulose– Furans, cyclopentanones

CH3 O

3-methylcyclopent-2-en-1-one

Bio-oil

– Open chain acids, aldehydes, ketones and alcohols

• Lignin– Alkyl, methoxy, carbonyl and

hydroxy substituted phenols

OHO

O

5-(hydroxymethyl)furan-2-carbaldehyde

CH3

OOH

1-hydroxypropan-2-one

O

OH

CH3

acetic acid

OH Ohydroxyacetaldehyde

CH3O

O

OH4-hydroxy-3-methoxybenzaldehyde

The distribution of products and their composition can be modified by the use of catalysts (various types of zeolites)

Catalytic pyrolysis

yp )

6

8

10

12

yiel

d w

t-%

H-Beta-25 H-Y-12 H-ZSM-5-23 H-MOR-20 Quartz

0

2

4

Aldehydes Acids Alcohols Ketones Phenols PAHs

y

A. Aho, N. Kumar, K. Eränen, T. Salmi, M. Hupa, D.Yu. Murzin, Catalytic pyrolysis of biomass in a fluidized bed reactor: influence of acidity of H-beta zeolite, IChemE, part B, Process Safety and Environmental Protection, 2007, 85, 473-480.

9

• Poor volatility, high viscosity, coking, i d ld fl bl

Problems with bio-oil

corrosiveness, and cold flow problems• In diesel engines: difficult ignition (due

to low heating value and high water content), corrosiveness (acids), and coking (thermally unstable components)components).

• Bio-oil upgrading (catalytic) is needed– hydrodeoxygenation– zeolite upgrading via cracking

– Zeolites as bed material providing heat and upgrading

Catalytic pyrolysis

providing heat and upgrading products

– Separation of pyrolysis and catalytic upgrading

Heat

Fluidization gas

Atte Aho

10

gases to coolers

Thermal pyrolysis and catalytic upgrading

pyrolysisreactor biomass

feeding

catalyticup-grading

g

gas heater

g

inlet forfluidizationgas

thermocouples in-pyrolysis reactor-up-grading reactor

Homogeneous hydrolysis

11

• Acid recovery• Corrosion

Drawbacks

• Chemical waste produced in – neutralization of acid– removal of degradation products

12

glucosecellulose

β bonds С1 -С4

Cellulose

Hydrogen bond

No space around bridge oxygen – penetration of homogeneous or heterogeneous catalyst difficult-Soluble in strange solvents (IL or ZnCl2)

Cellulose,Hemicellulose Hydrolysis Oxidation

S id

HydrolysisO

OOHO

O

HMF furfural

Dehydration

Aldoses

Sugar alcohols

HydrogenationFermentation

Sugar acids

Oligomers

Pentoses

IsomerizationEthanol

E t ifi ti

Aqueous reforming

Fuels

LubricantsChemicals

O

OH

OH

OHOH

xylose

Esterification

13

Results

Hydrolytic hydrogenation

A Fukuoka P L Dhepe Angew Chem Int Ed 2006 45 5161

A. A. Balandin, N.A. Vasyunina, S.V. Chepigo, G. S. BaryshevaDoklady Akademii Nauk SSSR, 1959, 128, 941

A. Fukuoka, P.L. Dhepe, Angew. Chem. Int. Ed. 2006, 45, 5161

14

Reagent• Cellulose

– Birch (Betula)Birch (Betula)– Finnish pulp mill (Metsä Serla)– 0.25 mm– Degree of polymerization

• 1900 (viscosity measurement) • Birchwood: 9400

Birch

Mats Käldström

15

O OH

OH

OH

OHOH OH

OH

OH

OHH2

DehydrocyclizationXylose Xylitol

H2O, H2

CatalystXylitol

Cellulose

OH

O

OO

H2

Furfural Furfuryl alcohol

Tar

OHO

OH

OH

OH

OH

OH

OH

OH

OH

OH

OHH2

H2O, H2

Catalyst

Pulp mill Cellulose

Decarboxylation

Tar

OH OH

OHO

O

DehydrocyclizationGlucose Sorbitol

5HMF

Sorbitol

M. Käldström, N. Kumar, M. Tenho, M. V. Mokeev, Y. E. Moskalenko, D. Yu. Murzin, ACS Catalysis (inpress).M. Käldström, N. Kumar, D. Yu. Murzin, Catal.Today, 167 (2011) 91.

30

16

• Cellulose 41%

Birchwood

• Hemicellulose 34 % Glucose

• Lignin 22 %

Xylan Xylose

0.12

Molar fraction

X l

Pt-MCM-48-imp O OH

OH

OH

OHOH OH

OH

OH

OH

OH

O

OO

H2

Dehydrocyclization

H2

Xylose XylitolH2O, H2

Catalyst

Furfural Furfuryl alcohol

Tar

OHOH

H2O, H2

Catalyst

Pulp mill Cellulose

Decarboxylation

Tar

Xylitol

0.06

0.08

0.1

Xylose

5HMF

Xylitol

OHO

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OHO

O

H2

Dehydrocyclization

Glucose Sorbitol

5HMF

Sorbitol

0

0.02

0.04

0 200 400 600 800 1000 1200 1400

Time, min

XylitolFurfuryl alcoho

Sorbitol

Furfural

Glucose

17

• Ball milled cellulose

Feedstock

• Kraft pulp cellulose • Hemicelluloses (should be extracted first!)

G l G l G l G l G l G lG l

GlcA

Ara

Ara

Arabinogalactans

Gal

• Backbone: β-galactopyranose• D-galactopyranose, L-arabinofuranose and D-

Gal Gal Gal Gal Gal GalGal

Gal Gal

Gal

Ara Ar

a Ara

glucuronic acid side chains.

• Potential for many products !Ara:Gal:GlcA ~ 19:80:2Molar mass 20,000 – 100,000

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Hydrolysis

O

OH

OH

OO

OH

O

OH

OH

O

O

O

OH

OH

O

O

O

OH

OH

O

O

O

OH

OH

O

OH

..

O

OH

OH

OH

O

OOH

OH

OH

O

OH

OH

OH

OH

OOH

OH

OH

O

OHOH

OH

OH

O

OH

OH

OHOH

OH

+[H+]

H2O

Steric hindrance of side chain no crystallinity easier to cleave

6080

100

120

140160180

200

C, m

g/g

HCICat ACat S

Arabinose

300

400

500

600

700

800

900

1000

C, m

g/g

HCICat ACat S

Galactose

HCl

SmopexAmberlyst

[H+]

HCl

y y

Selective cleavage

Bright Kusema

0 200 400 600 800 1000 1200 1400 16000

20

4060

Time, min0 200 400 600 800 1000 1200 1400 1600

0

100

200

300

Time, min

AmberlystSmopex Amberlyst

B. T. Kusema, G. Hilmann, P. Mäki-Arvela, S. Willför, B. Holmbom, T. Salmi, D.Yu. Murzin, Catalysis Letters, 2011, 141, 408-412

Hydrolytic hydrogenationBi-functional catalytic strategy, one-step transformation– Hydrolysis combined with hydrogenation– Heterogeneous catalyst, water as solvent

Cleavage of the glycosidic bonds to form sugars– Brønsted acidity

36

Hydrogenation of the sugars to polyols– Ru or PtCellulose/Hemicellulos

eSugars Polyols

Hydrolysis Hydrogenation

19

Results

60

80

%

H+

H+

Arabinogalactan

OO

OO OH

Arabinose Furfural

Decarbonylation

O

OH

OH

OHOH

OH

O

O

OH

OH

OH

O

OH

OH

OO

O

OHOH

OH

OH

H2O

H2O

- H2O

- H2O

0

20

40

Furfural+5-HMF

Pro

duct

yie

ld, %

Arabinose+Galactose

Galactose 5HMFOH

37

H-Beta-11 at 185°C and 20 bar H2

Arabinogalactan cleaved to form sugars

0 200 400 600 800 1000 1200 1400 16000

Time, min

Influence of support material

80

100

0

20

40

60

Con

vers

ion,

%

38

Arabinogalactan conversion after 120 minReaction conditions: 185°C, 20 bar H2

Highest Brønsted acid sites

H-Beta-11 H-Beta-25 H-Beta-300 H-MCM-48 Non-catalytic

20

Influence of metal

40

60

ld, %

O H

O H

O HO H

HOO H

G alactose

G alactitol

H 2

O

O H

OH

O HOH

O H

R u

HOO H

O H

O HO H

Arabinose

Arabitol

H 2

O

O HOH

O H

OH

Ru

0

20

Pro

duct

Yie

Arabinose + Galactose

Arabitol + Galactitol

Furfural + 5-HMF

Arabinose

39

5 wt. % Ru/Beta-11 at 185°C and 20 bar H2

Further hydrogenation of sugars into polyols

0 200 400 600 800 1000 1200 1400 1600

Time, min

Influence of metal

20

25

30

%

OO

Arabinose Furfural

O

OHOH

OH

OH

- H2O

5

10

15

20

Furfu

ral Y

ield

,

H-MCM-48

Pt MCM 48 Ru-MCM-48

OO OH

Galactose 5HMF

O

OH

OH

OHOH

OH

- H2O

40

0 200 400 600 800 1000 1200 1400 16000

Time, min

Pt-MCM-48 Ru-MCM-48

21

CO2 + H2Selective oxidation

Transformation of monomers

O

H

OHOH

H

H

OHH

OH

2 2Reforming

AraboketoseArabinitol

Speciality chemicals

IsomerizationHydrogenation

FurfuralPropandiol Glycerol

C-C hydrogenolysis

Ru/C (Sibunit)

Hydrogenation

O

OH

OH

OH

OH

OHOH

OH

OH

OHOH

OH

D-Galactose D-Galactitol

Victor Sifontes

22

Three-phase continuous system:Monolithic catalysts and microreactors

Three-phase continuous system:Monolithic catalysts and microreactors

• Ru over sibunit monolithic catalysts

• Reduction of the sugar to produce polyols (sugar alcohols)

Sugar hydrogenation

(sugar alcohols)• 2.5% Ru/C

H OH H OHOH OH

O

OHOH

HH

H

H

HOHOH OH

OOH

HH

H

H

OHOH

OH

OH

OHOH

OHOHRu/C

23

R /C h t b ff ti t l t f th

Hydrogenation of sugars: Some conclusions

• Ru/C has proven to be an effective catalyst for the reaction

• 100% conversion is achievable• Very good selectivity towards the sugar alcohols

(desired products).• Reaction rate increases with higher temperatures

and pressures• Hydrogenation reactions well described by the

models

Xylitol

24

• Cyclic vs acyclic formInfluence of the sugar structure

Mechanistic questions

• Influence of the sugar structure• Structure sensitivity• Hydrogen adsorption type• Reaction pathway

CO2 + H2Selective oxidation

Transformation of monomers

O

H

OHOH

H

H

OHH

OH

2 2Reforming

AraboketoseArabinitol

Speciality chemicals

IsomerizationHydrogenation

FurfuralPropandiol Glycerol

C-C hydrogenolysis

25

Oxidation of sugars

O HOHH

OHO

OHH

OH

O O

OH

OH

OH

+O2

Bright Kusema

Arabinose oxidation

OHHOH

HHOH

HO

OHOH

OH

arabinolactone arabinonic acid

26

DPU

Preparation

2 wt. % Au/Al2O3

Washing agent (H2O, NH4OH)

Initial t ti

51

DIE concentration (HAuCl4)

Calcinationtemperature(300-600ºC)

0.006

0.007

Activity dependence on cluster size

0.002

0.003

0.004

0.005

Rat

es, m

ol/g

*s

0 2 4 6 8 10 12 14 16 18 20 220.000

0.001

Au, nmO.A. Simakova, B. Kusema, B. Campo, A.-R. Leino, K. Kordas, V. Pitchon, P. Mäki-Arvela, D. Yu. Murzin, Journal of Physical Chemistry C , 2011, 115, 1036-1043

27

CO2 + H2Selective oxidation

Transformation of monomers

O

H

OHOH

H

H

OHH

OH

2 2Reforming

AraboketoseArabinitol

Speciality chemicals

IsomerizationHydrogenation

FurfuralPropandiol Glycerol

C-C hydrogenolysis

Aqueous phase reforming (APR)

Catalyst 1

J.A. Dumesic

APR

cellulose

Catalyst 2

Catalyst 3

28

Aqueous phase reforming of polyols

A.V. Kirilin, A.V. Tokarev, L.M. Kustov, T. Salmi, J.-P. Mikkola, D.Yu. Murzin,Aqueous phase reforming of xylitol and sorbitol: comparison and influence ofsubstrate structure, Applied Catalysis. A. General, 2012, 435-436, 172-180.

29

HPLC analysis of APR productsProducts separation using routine method for sugars:

5 8

4 8

5 0

5 2

5 4

5 6

mV

Conditions: Aminex HPX-87C (carbohydrate column), 80ºC, 0.4 ml/min 0.002 M CaSO4

2 0 3 0 4 0 5 0 6 04 4

4 6

t im e , m in

HPLC analysis of APR productsSeparation at optimal conditions:

5 1

5 2O

OH

4 7

4 8

4 9

5 0

5 1

mV

?

?

?

Column: Aminex HPX-87H (organic acid analysis), Eluent: 0.005 M H2SO4, 0.4 ml/min, 45ºC.

1 0 2 0 3 0 4 0 5 0 6 0 7 0

4 6

4 7

t im e , m inCH3OH

?

30

Liquid phase

isosorbideA. Kirilin

Some reactions in xylitol APR

31

Turpentine

Extractives

Chem.pulping

Paper&

BoardMech

Chem.pulp(Cellulose)

Turpentine

LigninHemicellulose

Mech

Chips

Tall oil

BoardMech.pulping

Mech.pulp

Knots LignansFlavonoidsStilbenes

Functional foodPharmaceuticalsNatural antioxidants & biocides

Tall oil

Resinous yellow-black oily liquid composed mainly of a mixture of rosin acids, fatty acids and sterols; obtained as a byproduct in theas a byproduct in the treatment of pine pulp.

32

Triglyceride

CH2── O ── C ── R′O

O het. cat.

Renewable source

Deoxygenation

Fatty acid ester

CH── O── C── R′′

CH2── O ── C ── R′′′

O

CnH2n+1── O ── C ── R′

O

het. cat.

het. cat.

3CO2 + R′-H + R′′-H + R′′′-H + light CXHY

CO2 + CnH2n + R′-H

Biodiesel

Animal fats & vegetable oils

Wood

Fatty acid

H── O ── C ── R′

Ohet. cat.

CO2 + R′-H

CnH2n+1 = Ester alkyl group (C1-C4), R′, R′′, R′′′ = Fatty acid alkyl chain, (saturated and unsaturated, C5-C23)XVIII International Conference on Chemical Reactors CHEMREACTOR-18 September 29 - October 3, 2008, Malta

Mathias Snare, Irina Simakova

Reaction mechanism

64

33

Forgotten knots

Knot – the branch base inside the stem

Knots: nature´s richest source of antioxidants

0.0 %0.1 %0.1 - 5 % 6 - 24%Lignans in spruce trees

70-85% of the lignansO

MeO

Hydroxymatairesinol (HMR)

O

OH

OH

OMe

OH150-200 tons/a in one pulp mill

34

O

OH

MeO

OMe

O

OH

HMR

O

OHOH

MeOMeO

OMeOMe

O

OHOH

HMROHOHOH

67

Markus, Mäki-Arvela, Kumar, Heikkilä, Lehto, Sjöholm, Holmbom, Salmi, Murzin, Reactions of hydroxymatairesinol over supported palladium catalysts, Journal of Catalysis, 2006, 238, 301-308

Hydrogenolysis and dehydrogenation of HMR

OxoMAT

N , Pd/CNF2

O

O

OH

HO

H3CO

OCH3

O

Desired products

Oxomatairesinol (oxoMAT)under nitrogen flow PdUnder air - Au

Journal of Catalysis, 2006, 238, 301 308

HMR7-i-propoxyMAT MAT

2-propanol, CNF H , Pd/CNF2

H7C3O

O

OH

HO

H3CO

OCH3

O

HO

O

OH

HO

H3CO

OCH3

O

O

OH

HO

H3CO

OCH3

O

ReactantMatairesinol (MAT)under hydrogen flow

35

O

OMeO

OHOH

O

OMeO

OH

Hydrogenolysis

From HMR to MR

OH

OMe

OH

HMR

OH

OMe

Matairesinol (MR)

More stable than HMRMore stable than HMRDifficult to isolate

Almost 100% selectivity

Research on biomass catalytic trans-formations should consider the process in its

Conclusions

formations should consider the process in its entity,

catalytic reactions per se feedstock purification/separation separation of productsseparation of products