Advanced catalytic processes in biorefinary of lignocellulosic biomass

Advanced catalytic processes in biorefinary of Advanced catalytic processes in biorefinary of lignocellulosic biomasslignocellulosic biomass

B.N. Kuznetsov

Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia

Siberian Federal University, Krasnoyarsk, Russia

Institute of Chemistry and Chemical Technology SB RAS Siberian Federal University

Presentation outlinePresentation outline1. Introduction

2. Catalysis in biorefinary

3. Gaseous and solid fuels from wood biomass

4. Liquid fuels from wood biomass

5. Chemicals from wood biomass

6. Integrated processing of wood biomass

7. Conclusive remarks

"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

1. Introduction

Biomass is an important feedstock for the renewable production of fuels, chemicals, and energy.

The worldwide production capabilities for renewable and sustainable biomass production are enormous. In the United States over 370 million dry tons and 1 billion dry tons of annual biomass are obtainable from forest and agricultural lands, respectively. Similarly large biomass production capacity is available in Europe, which could produce 190 million tons of oil equivalent (Mtoe) of biomass with possible increases up to 300 Mtoe by 2030.

Russia has around 23 % of world resources of wood and a half of this amount is located in Siberia, therefore in our country the wood biomass is the most suitable resource for bioproducts.


Characteristics of the siberian wood species

Type of wood

Elemental composition, % wt.a Chemical composition, % wt.

C H N S O Cellulose Lignin Hemicelluloses

Pine wood

47.4 6.2 0.4 0.2 45.8 48.2 29.4 15.3

Aspen wood

47.5 6.1 0.2 0.1 46.1 46.3 21.8 24.5

Beech wood

45.9 6.0 0.2 0.2 47.7 46.4 25.3 22.4

Spruce wood

46.3 6.8 0.3 0.1 43.2 50.3 27.7 15.4a Dry ash-free basis


2. Catalysis in biorefinary

Over the 20th century, the

petrochemical and the chemical

industry developed numerous catalytic

processes to transform

hydrocarbon-like compounds into great

number of products. However, most of

these processes are not suitable for

converting biomass.

In biorefinery, processing starts from

highly oxygenated raw materials, and

controlled catalytic de-functionalization

is necessary, instead of

functionalization used nowadays in the

chemical industry.

The O/C and H/C molar ratios of fossil and biomass raw materials and of fuels derived from them



Application of solid catalysts in biomass processing

Advantages of the heterogeneous catalysis processes over homogeneous processes :

– easy separation of products and catalyst,

– less corrosive activity of reaction mixture,

– easy regeneration of the catalyst,

– better regulation of catalyst performance owing to the wider range of reactions condition.

The next ways are used to increase the efficiency of biomass processing:

1.Selection of the effective catalysts for polysaccharides conversion.

2.Using of effective methods of biomass activation and fractionation.

3.Integration of production of chemicals and biofuels in the combined technological cycle.

This presentation describes the results of study of advanced catalytic processes in biorefinary of wood biomass obtained in the ICCT SB RAS and SFU.

At present the ecology dangerous and corrosive active

catalysts on the bases of inorganic acids and alkali

solutions are mainly used in biomass conversions.

These catalysts should be changed on the more

technologically suitable solid acid catalysts and on

bifunctional catalysts.

Processes of plant biomass conversion to the more usable energy forms


Plant biomass

Thermal liquefaction

Gasification Pyrolysis Hydrolysis Fermentation

ExtractionEtherification

Liquid fuels Gaseous fuels

SolidLiquid

Gaseous Fuels

BiodieselEthanolButanol

3. Gaseous and solid fuels from wood biomass


Scheme of autothermal carbonization of biomass in a fluidized bed of oxidation catalyst

Powdery biomass

Air

Gas Char

Fluidized

bed of

catalyst


Product cooling

Char combustion and gasification

Char formation

Volatiles evolution and oxidation by

catalyst

Biomass heating

Some advantages of the autothermal carbonization process

• the process proceeds in autothermal

conditions without additional heat

supply, resulting in less number of

apparatus in technological scheme;

• the process productivity is higher in

comparison with conventional

pyrolysis methods owing to fluidized-

bed technology;

• the variation of carbon products

structure and properties is possible in

broad limits;

• no pyrolysis tar is formed and

gaseous product contain a reduced

concentration of harmful compounds.


Parameters of thermal treatments of lignin in fluidized bed of oxidation catalyst and yields of char

Parameter of the process

Experiment number

1 2 3 4 5 6 7 8 9

Quartzsand

Al-Cu-Cr oxide catalyst

Flow rate of gases (m3 / h) 95.1 94.8 100.3 108.9 110.3 110.9 111.0 109.9 153.8

Composition of reaction mixture

Lignin (kg/m3 ) 0.32 0.35 0.21 0.12 0.23 0.18 0.25 0.41 0.12

Oxygen (% vol) 13.7 13.4 5.8 5.1 5.8 6.5 8.8 11.5 6.9

Water/steam (% vol) 34.8 36.1 21.9 36.2 21.9 33.7 32.7 45.4 35.3

Carbon dioxide (% vol) - - 7.8 6.2 7.8 5.5 3.8 - 4.3

Temperature of bed (O C) 770 820 760 785 770 800 780 670 815

Yield, kg/kg 0.18 0.20 0.16 0.19 0.15 0.20 0.24 0.28 0.21

Properties of char products obtained by lignin carbonization in a fluidized bed of catalyst

Indices

Experiment number

1 2 3 4 5 6 7 8 9

Quartzsand

Al-Cu-Cr oxide catalyst

Porosity (cm3 /g) 1.62 1.79 1.58 1.73 1.88 1.71 1.72 1.81 2.15

Surface area (m2 /g) 12 64 72 110 - 144 - 22 86

Ash content (%) 18.2 16.7 21.1 17.4 21.5 16.2 13.5 12.1 16.1

Ash content in fraction of particles > 0.2 mm (%) 12.3 7.2 11.8 8.8 11.4 7.4 7.7 7.5 8.3

I2 sorption ability (%) 6 25 33 42 33 43 30 7 38


The advantages of developed

process :

• Supply by recirculated char

particles up to 70-90 % energy

demanded for autothermal

regime of gasification process

• Significant decrease of the

consumption of expensive

oxygen

• Low concentration of tar in

produced syn-gas; this facilitate

its purification and increases the

process ecological safety

Syn-gas and fuel gas producing from powdery biomass in fluidized bed of

catalyst

700-750 °C

Steam Oxygen

Fuel gas

Air Biomass

Pyrolysisreactor

Gasificationreactor

850-900 °C

Fluidized bed of catalyst

Char Syn-gasCO+H2

Recirculatedparticles


Char materialTemperature,

°СH2 content,

% vol.Tar content,

g/nm3

Heat of combustion,

MJ/nm3

From lignite 670-750 50-60 следы 10,5-11,1

From birch wood 620-710 58-65 1,0 10,2-10,8

From hydrolysis lignin

670-780 52-59 следы 10,2-10,5

Wood and agricultural wastes

650-780* 35-57* 20-70* 11,8-13,8*

Gasification of char materials by water-steam in fluidized bed of Martin slag

Steam gasification of char produces gas with H2 content 60-65 % vol. and very low amount of tar impurities.


* Literature data

steam

А

Methan-containing gas

Wood sawdust

9

5

8

4

1

3

7

2

6

air

S m o ke gases

Scheme of methane production by wood gasification in fluidized bed of methanization catalyst

1 – feeder, 2 – methanization reactor, 3 – fluidized bed of catalyst, 4 – gas distribution grid, 5 – build-up cyclone, 6 – pipe for char product, 7 – fluidized bed of char product, 8 – combustion chamber, 9 – injector for air supply.

Wood particles feeding to heated at 500-600 °C fluidized bed of catalyst expose to destruction with the formation of volatiles and char products. Some part of the char reacts with steam the another is burned in the combustion chamber.The heat for gasification process is collected from three main sources including: overheated water-steam, methanization reactor and combustion chamber.


0

20

40

60

80

100 A

ctiv

ity, %

1 2 3 4 5 Samples

Catalytic activity of metallurgical slags materials in reaction of methanization of the mixture CO + H2 + H2O:

1 – commercial catalyst ANKM-1E, 2 – converter slag, 3 – steel-smelting slag, 4 – Martin slag, 5 – activated Martin slag

Influence of conditions of wood sawdust gasification on the yield and composition of produced gases

IndicesBirch sawdust in bed of

quartz sandBirch sawdust in bed of

activated Martin slagAspen sawdust in bed

of activated Martin slagSteam consumption (420°С) kg/kg sawdust

1.7 1.2 1.2

Temperature in the upper bed of slag, °C 650 655 660Yield of dry gas, m3/kg sawdust 0.68 0.58 0.60Composition of dry gas, % wt.H2 22.3 17.9 16.4CO 5.8 1.2 1.9CH4 27.8 42.8 41.3CnHm 2.1 2.4 1.9CO2 39.6 34.5 33.8N2 2.4 1.2 4.7Heat of combustion of dry gas, kJ/nm3 14150 18600 17800

The developed gasification process makes it possible to produce from waste wood the methane-containing gas with calorific value on 30 % higher in comparison with the traditional steam gasification process. Besides, the part of potential heat of the initial raw material, transforming to the potential heat of the produced gas was increased by 10 relative %.


4. Liquid fuels from wood biomass


At the present time, two biomass-derived fuels (so-called first generation of biofuels) have been successfully implemented in the transportation sector:

biodiesel (a mixture of long-chain alkyl esters produced by transesterification of vegetable oils with methanol)

bioethanol (produced by fermentation of corn and sugar cane-derived sugars).

The current biofuel market is largely dominated by ethanol, which accounts for 90% of world biofuel production. Indeed, the rate of ethanol production around the world is increasing rapidly.

The urgent task is the development of bioethanol production from non-food lignocellulosic biomass.

Wood hydrolyzates of the traditional hydrolysis industry have complex composition and they contain different impurities which inhibits the sugar fermentation process.

Different approaches are used to increase the quality of wood hydrolyzates.

The key of them should include the preliminary separation of wood on cellulose, hemicelluloses and soluble lignin.

Two-stage hydrolysis for ethanol production from plant biomass

Influence of composition of the hydrolyzates on the yield of ethanol

Biomass type

Composition of hydrolyzate, % Ethanol yield, % wt.

One-stage hydrolysis

Two-stage hydrolysis One-stage

hydrolysisTwo-stage hydrolysis

C6-sugars C5-sugars C6-sugars C5-sugars

Aspen wood 49.4 18.8 43.8 - 19.9 26.8

Wheat straw 37.3 14.2 35.1 - 14.8 21.4

C5-sugars removal at the pre-hydrolysis stage increases on 30-35 % the yield of ethanol.

Wood

Hydrolysis by 70 % H2SO4 and inversion

Pre-hydrolysis 2 % HCl

Hydrolyzate C5 – sugars

Pre-hydrolyzed wood

EthanolFermentation


Scheme of ethanol production from wood

Conditions of glucose fermentation:• temperature 34 – 36 °C,• amount of yeast 3 – 5 g,• ferment saccharomyces cerevisiae,• time of treatment 5 h,• volume of hydrolyzate 0.1 l

Wood sawdustWood sawdust

Catalytic fractionation of main components or explosive autohydrolysis

Products from hemicelluloses and

amorphous cellulose

Products from hemicelluloses and

amorphous cellulose

CelluloseCellulose Low molecular mass lignin

Low molecular mass lignin

Catalytic hydrolysis

Fermentation

Solution of glucoseSolution of glucose

EthanolEthanol

Preliminary separation of cellulose from wood increases the quality of hydrolyzates as compared to direct hydrolysis of wood. This simplifies the fermentation process and it results in the increase the yield of bioethanol.



Instead of using biomass to produce oxygenated fuels (such as ethanol) with new compositions, an attractive alternative would be to utilize biomass to generate liquid fuels chemically similar to those being used today derived from oil.

These new fuels would be denoted as green gasoline, green diesel and green jet fuel.

The most simple way of liquid hydrocarbon producing is the pyrolysis of biomass with following upgrading of bio-oils.

Hydrocarbons motor fuels from lignocellulosic biomass

Multistep scheme of lignin hydroliquifaction to green fuels and oxygenates

Lignin Phenolic Intermediates

Naphthenicfuel additive

Aromatic fuel additive

Oxygenatefuel additive

Base Catalyzed Depolymerization

(BCD)

Hydrodeoxygenation(HDO)

Hydrodeoxygenation(HDO)

Selective Hydrogenolysis

(HT)

Etherification

Hydrocracking(HCR)

Selective RingHydrogenation

(SRH)


Biomass liquefaction without expensive hydrogen application

Lignin catalytic liquefaction in methanol:

Proposed mechanism of liquefaction:

Lignin + Methanol380-410 °C

LiquidsFe-Zn-Cr

Fe-Zn-CrCH3OH + H2O 3H2 + CO2

Lignin + H2 Product - Ar - H

Product-Ar-H + CH3OH Product-Ar-CH3 + H2O

Yield of liquid hydrocarbons 40-45 % mas.

Wood biomass liquefaction by melted formate/alkali mixtures and with the use of metallic iron/Na 2CO3 system is carried out at low pressures. But these methods give only moderate yield of bio-liquids. The highest yield of bio-liquid was obtained in the process of biomass dissolvation in methanol media in the presence of Zn-Cr-Fe catalyst at 20 MPa.

Pyrolysis by metallic iron, promoted by Na2CO3:

Metallic iron regeneration:

FeO + C0.1MPa

600 °CFe + CO

Yield of liquid products 14% mas.

Biomass400-600 °C

FeO + C + Oil product Fe

Liquefaction by melted alkali formate:

The highest yield of oil (16.4 % mas.) was observed at 400 °C

Biomass + Melted alkali 300-450 °C

Oil product

Kuznetsov B.N. Int. J. of Hydrogen Energy (2009)


Liquefaction of wood/plastics mixturesPolyolefines contain rather high amount of hydrogen and they provide hydrogen at thermal co-processing with biomass increasing the yield of liquid hydrocarbons.It was established the influence of co-treatment process conditions on the yield and composition of liquid products:• process operating parameters (temperature, gaseous medium, time of treatment, biomass/plastic ratio);• nature of plant biomass (cellulose, lignin, beech-wood, pine-wood);• nature of plastics (polyethylene, isotactic-polypropylene, atactic-polypropylene);• addition of iron-ore catalysts.

The highest yield of light hydrocarbons is observed for cellulose, the lowest – for lignin. The influence of biomass nature on the yields of light liquid fraction is more pronounced than that of polyolefin origin.

Sharypov V.I., Beregovtsova N.G., Kuznetsov B.N. et. al. J. Sib. Fed. Univ. Chem. 2008)

Influence of polymer nature on the yield of liquid products of beech/polyolefine

(1:1) mixture pyrolysis at 400 °C

0

5

10

15

20

25

iPP aPP PE%

wt.

12

12

1

2

Influence of biomass origin on the yield of liquid products of biomass/aPP (1:1)

pyrolysis at 400 °C

Light liquidHeavy liquid0

5

10

15

20

25

30

35

Cellulose Beechwood

Pinewood

Hydrolyticlignin

(1 – fraction < 180 °C, 2- fraction > 180 °C)


0

2

4

6

8

10

12

14

16

6 7 8 9 10 11 12 13

Number of carbon atoms in the molecule

% m

as.

0

5

10

15

20

25

30

% m

as.

А

1

2 3

4

5

0

5

10

15

20

25

5 6 7 8 9 10 11 12

Number of carbon atoms in the molecule

% m

as.

0

5

10

15

20

25

30

35

40

% m

as.

1

2

34

5

B

GC-MS data on the distribution of hydrocarbons in the light liquid fraction

(b.p. below 180 °C) of mixtures (1:1) pine-wood/polyethylene (A) and pine-wood/polypropylene (B) hydropyrolysis

1 – parafins, 2 – cycloparafins, 3 – olefins, 4 – aromatic compounds, 5 – total contents of C5-C13 hyrocarbons

According to GC-MS data the light liquids of biomass/plastic hydropyrolysis contain mainly normal paraffines C7-C13 (about 75 % for pine-wood/PP mixture), alkylbenzenes and alkylfuranes compounds (about 10 %) and non-identified compounds (about 15 %). Sharypov V.I., Beregovtsova N.G., Kuznetsov B.N. et. al. J. Anal. Appl. Pyrolysis (2006)



Lignin catalytic depolymerization in ethanol medium over acid zeolite catalysts

Temperature, °C

Zeolite catalysts in H-form

Conversion, % wt.

Yield of products soluble in ethanol, % wt. Yield* of gaseous

products, % wt.< 180 °C > 180 °C

300

absent 50 30.1 13.1 1.6HY 56 33.2 17.5 1.8

Si/Al-30 62 25.1 31.8 2.3Si/Al-100 49 22.2 21.7 2.0

350

absent 53 30.9 16.0 3.2HY 62 30.7 25.2 3.8

Si/Al-30 71 44.3 20.6 4.9Si/Al-100 64 35.0 22.9 4.5

400

absent 49 27.4 9.2 4.1HY 53 26.7 14.2 5.3

Si/Al-30 55 28.6 14.0 5.8Si/Al-100 53 26.8 13.9 4.9

The maximum conversion of lignin (71 % wt.) and the high yield of light fraction (< 180 °C) of liquid products (44 % wt.) were observed at 350 °C in the presence of zeolite catalyst with Si/Al ratio 30.


Composition of liquid products of lignin conversion in ethanol over zeolite catalysts at 400 °C (CMS data)

ProductsContent, %

Without catalyst НУ HSZ-30 HSZ-100

Alkanes, alkenes <0,1 0,1 0,2 15,2Acids, aldehydes, ketones, acetals 4,9 8,4 3,2 1,4

Esters 5,5 3,9 14,8 2,1Aliphatic alcohols 9,9 20,9 16,1 10,01,1-diethoxyethane 1,2 41,7 59,1 51,3Benzene derivatives 5,8 6,0 1,8 2,4Phenol and its derivatives 72,7 19,0 4,5 15,4

Zeolite catalysts increase significantly (to 50 times) the content of 1,1-diethoxyethane and reduce by 4-16 times of phenol and its derivative in liquid products as compared to non-catalytic process.

Main components of wood biomass

Cellulose (C6H10O5)n – 40-50 %

Hemicellulose (C5H8O4)n – 15-30 %

Lignin – 16-33 %

Extractive compounds – 1-10 %

Lignin is non-regular polymer composed of

phenylpropane fragmentsCHO

H-C-H

H-C-H

OMeHC - O

HOH 2C

- Ar - O - C - H

MeOO - CH 2

HC

HC - O

HOH 2C

H(C 6H10O5)n-O-CH

OMe

HC O

HC

CH 2OHCH 2

HC

CH 2OH OMe

OH

Cellulose is a linear polymer, constructed from C6-units

HO

H H

OH H

H OH

H

O

H

O

O

H OH

OH H

H

CH 2OH

O

H HO

CH 2OH

H

OH H

H OH

H

O

CH 2OH

CH 2OHO

OH

H

H

OH H

H OH


4. Chemicals from wood biomass

H

H H

O OH H

CH 2 OH

H OH

O

H O O

O

C-H

O

HOH 2 C

Hydroxymethylfurfural

H 2 C O

H

H O

O

Levulinic acid

CH 3 - C - CH 2 - CH 2 - C - OH

H

H

HO OH H

CH 2 OH

H OH

OH

Cellulose Glucose Levoglucosenone

n

Scheme of cellulose transformation in the presence of acid catalysts


Chemical products from glucose

J. N. Chheda, G. W. Huber, J. A. Dumesic, Angew. Chem. Int. Ed., 2007


O OH

OHHO

OH

OH

HOOH

O

O

OH

O

O

OHHO

Malic Acid

O

OH

O

HO

Succinic Acid

FumaricAcid

amination

O

OH

O

HO

NH2

Aspartic Acid

fermentationKrebs Pathway

O

OHHO

O O

2,5-Furandicarboxylic acid

HO OH

O

3-Hydroxypropionic acid

HOOH

O

O

NH2

Aspartic Acid

Glucose

fermentation

HOOH

O

OOItaconic acid

O

O OH

5-Hydroxymethylfurfural

dehydration

HO OH

O O

NH2Glutamic Acid

OO

HO3-Hydroxybutyrolactone

HOOH

OH

OH

OH

OH

Sorbitol

HOOH

OH

OH

OH

OH

OGluconic Acid

hydrogenationfermentation&oxidation

oxidation

dehydrationHO

O

OLevulinic Acid

HOOH

OH

OH

OH

OH

O

O

Glucaric Acid

Chemical and fuels from levulinic acid


Succinic Acid O

OH

O

HO

CHEMICAL INTERMEDIATES

O

Tetrehydrofuran

O OH3C

-valerolactone

SOLVENTS

H3C CH3

OH3C

5-nonanone

2-methyl-tetrahydrofuranFUELSH3C

O

O

O

CH3

Ethyl levulinate O OH3C

-angelicalactone

FOOD, FLAVOURING AND FRAGRANCE COMPONENTS

HOCH2

Acrylic acid

R

HO

H3C

R

Diphenolic acid

RESINS

PLASTICISERS

1,4-butanediol

C

OH

1,4-pentanediol

ANTI-FREEZE AGENTS

O

O

O

H3C Na

sodium levulinate

PHARMACEUTICAL AGENTS

O

O

HO Br

5-bromolevulinic acid

HERBICIDES

O

O

HO OH

O

-aminolevulinic acid

POLYMERS

NHNH

O

O

nNylon 6,6 (polyamide)

HO

O

OLevulinic Acid

Formation of acid groups SO3H and COOH in catalysts

Catalyst TreatmentSBA-15 Mercaptotrimetoxysilane +H2O2

Sibunit H2SO4 + K2Cr2O7

Sibunit H2SO4

TEG (thermally expanded graphite)

H2SO4


Proposed structure of carbon catalyst with –SO3H, –COOH and –OH groups*

* Satoshi Suganuma et.al. JACS. 2008.

The catalytic activity of carbon with SO3H, OH, and COOH groups in cellulose hydrolysis can be attributed to the ability to adsorb β-1,4 glucan.

Influence of catalyst nature on the conversion of cellulose in hydrolysis at 150 °C

Sulfated mesoporous SBA-15 catalyst has the highest activity (cellulose conversion 80 % wt.). It exceeds the activity of acid catalysts Nafion and Amberlyst-15.

Chemical and combined treatments of MCC increase its conversion in catalytic hydrolysis.

Influence of catalyst nature on the yield of glucose in cellulose hydrolysis at 150 °C (12 h) (catalyst/cellulose wt. ratio = 1)

HPLС analysis of products of MCC hydrolysis at 150 °C over sulfated SBA-15 catalyst

Products of MCC hydrolysis over SBA-15 two-stage synthesis contain mainly glucose.

0

10

20

30

40

50

60

70

80

90

Without catalyst SBA-15 two-stage synthesis

SBA-15 one-stage synthesis

TEG + H2SO4 Sibunit K2Cr2O7+H2SO4

Sibunit H2SO4 Nafion N551PW

Ce

llu

lose

co

nv

ers

ion

, % w

t.

Glu

cose

yie

ld, %

wt.

1

1

1

1

1

1

1

2

2 2

2

2

2

2

1 – cellulose conversion, 2 – glucose yield


Kinetic curves of levulinic acid (LA) formation from different substrates at 98 °C in the presence of HCl (3.8 M)

The maximum rates of the LA formation were observed for the fructose and sucrose. Cellulose and wood are less reactive, obviously according to the diffusion limitations during plant polymers hydrolysis.

0 100 200 3000

20

40

60

80

100

3

2

1

Yie

ld o

f L

A, m

ol.

%

Time, min0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0 100 200 300 400

Time, min

Co

nce

ntr

atio

n o

f L

A,

g/l

6

5

4

1 – sucrose, 2 – fructose, 3 – glucose, 4 – abies wood, 5 – aspen wood, 6 – cellulose

0

5

10

15

20

25

30

35

Lev

uli

nic

aci

d y

ield

, % m

ol.

Н3PO4 Н2SO4 НCl

Effect of the catalyst nature on the yield of levulinic acid from glucose at 98 °C and a Hammet acidity function of Ho = -2.6

Taraban’ko V.E., Chernyak M.Yu., Aralova S.V., Kuznetsov B.N. React. Kinet. Catal. Lett. (2002) "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

Yield of levulinic acid in thermocatalytic transformations of cellulose by steam

Without catalyst

H2SO4 Fe2(SO4)3 Al2(SO4)3

150 200 250 150 200 250 150 200 250 150 200 250

Yield of levulinic acid, % wt.

- - 0.6 - 22.1 25.2 - 1.8 4.7 - 16.6 18.4

Degree of the cellulose conversion, %

0.0 14.5 23.8 21.7 62.6 67.3 1.2 26.7 52.9 6.4 58.1 58.6

Yield of levulinic acid in thermocatalytic transformations of wood by steam in the presence of 5 % of H2SO4, % wt.

Temperature, °C Beech Aspen Pine Spruce

200 16.4 15.6 14.5 13.3

240 17.3 15.7 15.5 14.5


Acetylene, ethylene

Phenolic acids, catechol

Acetic acid, phenol, substituted phenols, CO, methane

Oxidized lignin for paints and coatings

Vanilic, ferulic, coumaric and other acids

Lignin with increased level of polymerization

Vanilin, demethylsulfide, methyl mercaptan, dimethyl sulfoxide

Phenol, substituted phenols

Phenols, cresols, substituted phenols

pyrolysis

fast thermolysis

alcali fusion

enzymatic oxidation

microbial conversions

oxidative

hydrolysis

hydrogenation

Products of lignin catalytic transformations


Yield of aromatic aldehydes at birch wood oxidation by molecular oxygen at 170 °C

in the presence of Cu(OH)2 catalyst

1– total yield, 2 – syringaldehyde, 3 - vanillin

0

10

20

30

40

50

5 15 25 35

Time, min

Ye

ld, %

on

lig

nin

1

2

3

Catalytic and non-catalytic oxidation of wood lignins to vanillin and syringaldehyde

Used ligninOxidation reagent

Catalyst

Yield, % mas. to lignin

Vanillin Syringaldehyde

Fir wood Nitrobenzene - 27.5 -

Fir wood Air - 11.4 -

Aspen wood

Nitrobenzene - 12.9 30.7

Aspen wood

O2 - 4.8 7.7

Aspen wood

Antraquinone 6.4 14.6

Aspen wood

O2 CuO 11 30

Softwood sulphite lignin

Nitrobenzene - 16.5 -

Softwood sulphite lignin (Syas Plant

Air - 3.5-4.5 -

Softwood sulphite lignin (Syas Plant

O2 Cu(OH)2 14.2 -

Softwood sulphite lignin (Monsano)

O2 Cu 10 -

Hardwood sulphite lignin

Nitrobenzene - 6.1 10.1

Kuznetsov B.N., Kuznetsova S.A., Danilov V.G., Tarabanko V.E. Chem. Sustain. Dev. (2005)


Some characteristics of the developed catalytic process of vanillin producing from lignosulphonates and the industrial

technology of Syas Plant

Process characteristics

Developed process

Syas Plant

Time of oxidation stage, h

0,2-0,3 3

Vanillin concentration, g/l

9-12 7-8

Lignosulphonates expenses, kg/kg vanilline

15-20 38

Coefficient of vanillin distribution at the extraction stage

10-15 6

Time of vanillin extraction, h

0,5-0,6 30


6. Integrated processing of 6. Integrated processing of lignocellulosic biomasslignocellulosic biomass


Carbohydrates and lignosellulosic materials

Pyrolysis/gasification Hydrolysis(enzymatic and chemical)

Syngas Bio-oilFermentation

Hydrogen Fuels Ethanol Platform molecules

Energy Chemicals

Biorefinery scheme described in the Biomass program of US Department of Energy

Biorefinary is described as a facility that integrates biomass conversion processes and equipment to produce fuel, power and chemicals from biomass.Biomass is converted to fuels via pyrolysis and gasification and the other part is converted by fermentation or chemo-catalytic routes to well-indentified platform molecules can be employed as building blocks in chemical synthesis.

Gallezot P. Catalysis Today (2007)


Scheme of integrated catalytic conversion of wood to liquid biofuels


Wood biomass

Catalytic oxidative fractionation

Soluble lignin Cellulose

Catalytic conversion

Liquid hydrocarbons

Catalytic hydrolysis

GlucoseBioethanol

Studied catalytic process includes the steps of oxidative fractionation of wood biomass into cellulose and soluble lignin, hydrolysis of cellulose to glucose, fermentation of glucose to bioethanol, conversion of lignin to liquid hydrocarbons.Main steps of integrated processing of aspen wood into valuable bio-products based on the use of solid catalysts were optimized.

Influence of aspen-wood delignification temperature on residual lignin content in cellulosic product (reaction conditions: H2O2 5 % wt., CH3COOH 25 % wt., catalyst TiO2 1 % wt., LWR

15)


Influence of temperature on cellulosic product yield and composition. Delignification conditions: CH3COOH – 25 % mas., H2O2 – 4 % mas., LWR 10, time 4 h, 1 % wt. TiO2

Temperature, °CYield of cellulosic

product, %*

Composition of product, % **

cellulose hemicelluloses lignin

70 76.7 75.1 8.3 15.6

80 72.8 84.3 8.0 6.3

90 60.8 90.3 7.7 1.3

100 50.2 91.1 7.4 0.6

SEM images of samples MCC “Vivapur” (А) and cellulose obtained from aspen- wood with TiO2 (B) catalyst

A B


0

200

400

600

800

1000

1200

1400

0 10 20 30 40 50 60

Inte

nsit

y

2 Theta

32

1

1

2

3

Diffraction patterns of cellulose from aspen wood obtained with H2SO4 (1), TiO2 (2) catalyst and industrial microcrystalline cellulose Vivapur (3)

According to SEM, FTIR and XRD data the structure of wood cellulose corresponds to microcrystalline cellulose.

Scheme of integrated conversion of lignocellulosic biomass into chemicals functional materials and biofuels

Lignocellulosic biomass

Separation

Lignin Nanoporous carbons

Cellulose

Liquid hydrocarbons

Sorbents Binding agents

GlucoseLevulinic acid

Modified cellulose

Wood composites

BioethanolBiodegradable polymersSolid

biofuels


Integrated processing of birch-wood to chemical products

Birch-wood

Acidic pre-hydrolysis at 98 °C

Pre-hydrolyzed wood

Catalytic delignification at 120-130 °C

Oxidation by O2 at 170 °C

Chemically pure cellulose

Phenolicsubstances

Microcrystalline cellulose

PhenolsAntioxidants

Aromatic compounds

Cellulose Vanillin

Syringaldehyde

Levulinicacid

Pentosanes

Xylite

Furfural

Yield of chemical products at integrated processing of birch wood

Product C5-sugars Microcrystalline cellulose

Vanillin Syringaldehyde Levulinic acidPhenolic

substances

Yield, % mas. 20.0 32.5 1.4 3.1 10.5 9.5


Yield of chemical products at integrated processing of larch wood

Product Arabinogalactan Dihydroquercetin Microcrystalline cellulose

Vanillin Levulinic acid

Phenolic substances

Yield, % mas. 18,1 0,6 31,2 5,4 8,6 11,9

Larch wood

Extraction by water at 100 оС

Extracted wood

Dihydroquercetin

Arabinigalactan

Catalytic oxidation by О2 at 170 °С

Catalytic delignification by H2O2 at 130 °С

Levulinic acid Cellulose Vanillin Microcrystalline cellulose

Phenolic substances

Kuznetsov B.N., Kuznetsova S.A., Tarabanko V.E. Russian Chem. J. (2004)


Integrated processing of larch-wood to chemical products

7. Conclusive remarks

There are potential analogies between the 20th century petroleum refinery and the 21st century biorefinery. Development of the petroleum refinery took considerable effort to become the highly efficient and many of the breakthroughs involved catalytic developments. The future success of biorefinery will require a design of a new generation of catalysts for the selective processing of carbohydrates and lignin.Ecology dangerous and corrosive-active catalysts on the bases of inorganic acids and alkali solutions should be changed on the more technologically suitable solid catalysts.The design of efficient multifunctional catalysts opens the new possibilities in biomass processing since they allow to carry out the multisteps transformations to the target products by one-stage conversion.The integration of different catalytic processes in one technological cycle allows to perform a wasteless processing of all components of lignocellulosic biomass to biofuels and platform chemicals .


Acknowledgements

Authors is grateful to team members

actively participating in the studies:

Prof. N.V. Chesnokov

Prof. S.A. Kuznetsova

Dr. V.I. Sharypov

Dr. V.G. Danilov

Dr. A.V. Rudkovsky

Dr. I.G. Sudakova

Dr. S.V. Baryshnikov

Dr. A.I. Chudina

Dr. O.V. Yatsenkova

Dr. N.M. Ivanchenko

N.V. Garyntseva

A.M. Skripnikov


Thank you for your attention!

Suburb of Krasnoyarsk


Date post:	31-Dec-2015
Category:	Documents
Upload:	danniell-klein
View:	33 times
Download:	2 times

Advanced catalytic processes in biorefinary of lignocellulosic biomass

Documents