1. Advanced catalytic processes in biorefinary of lignocellulosic biomass
Institute of Chemistry and Chemical Technology SB RAS
Siberian Federal University
Advanced catalytic processes in biorefinary of lignocellulosic biomass
B.N. Kuznetsov
Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia
Siberian Federal University, Krasnoyarsk, Russia

2. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Presentation outline
1. 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

3. "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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

4. 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
0.1
46.1
46.3
21.8
24.5
Beech wood
45.9
6.0
47.7
46.4
25.3
22.4
Spruce wood
6.8
0.3
43.2
50.3
27.7
15.4
a Dry ash-free basis
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

5. 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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

6. Application of solid catalysts in biomass processing
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.
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:
Selection of the effective catalysts for polysaccharides conversion.
Using of effective methods of biomass activation and fractionation.
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

7. Processes of plant biomass conversion to the more usable energy forms
Thermal liquefaction
Gasification
Pyrolysis
Hydrolysis Fermentation
Extraction
Etherification
Liquid fuels
Gaseous fuels
Solid
Liquid
Gaseous Fuels
Biodiesel
Ethanol
Butanol
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

8. 3. Gaseous and solid fuels from wood biomass
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9. Scheme of autothermal carbonization of biomass in a fluidized bed of oxidation catalyst
The main steps of biomass oxidative carbonization in fluidized bed of catalyst
Powdery biomass
Char and gases
Feeding by air through heated fluidized bed of the oxidation catalyst
Volatile compounds evolution
Carbonization and activation of char particles
Volatile compounds oxidation by the catalyst
Heat
Powdery biomass
Air
Gas
Char
Product cooling
Char combustion and gasification
Char formation
Volatiles evolution and oxidation by catalyst
Biomass heating
Fluidized
bed of catalyst
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10. 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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

11. 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
Quartz
sand
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
Oxygen (% vol)
13.7
13.4
5.8
5.1
6.5
8.8
11.5
6.9
Water/steam (% vol)
34.8
36.1
21.9
36.2
33.7
32.7
45.4
35.3
Carbon dioxide (% vol) -
7.8
6.2
5.5
3.8
4.3
Temperature of bed (O C)
770
820
760
785
800
780
670
815
Yield, kg/kg
0.20
0.16
0.19
0.15
0.24
0.28
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
Quartz
sand
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 (%) 25 33 42 43 30 38
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12. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Syn-gas and fuel gas producing from powdery biomass in fluidized bed of catalyst
The advantages of developed process :
Supply by recirculated char particles up to % 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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

13. Heat of combustion, MJ/nm3
Gasification of char materials by water-steam in fluidized bed of Martin slag
Char material
Temperature, °С
H2 content, % vol.
Tar content, g/nm3
Heat of combustion, MJ/nm3
From lignite
50-60
следы
10,5-11,1
From birch wood
58-65
1,0
10,2-10,8
From hydrolysis lignin
52-59
10,2-10,5
Wood and agricultural wastes *
35-57*
20-70*
11,8-13,8*
* Literature data
Steam gasification of char produces gas with H2 content % vol. and very low amount of tar impurities.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

14. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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 °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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

15. 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
Indices
Birch sawdust in bed of quartz sand
Birch sawdust in bed of activated Martin slag
Aspen sawdust in bed of activated Martin slag
Steam consumption (420°С) kg/kg sawdust
1.7
1.2
Temperature in the upper bed of slag, °C
650
655
660
Yield of dry gas, m3/kg sawdust
0.68
0.58
0.60
Composition of dry gas, % wt. H2
22.3
17.9
16.4 CO
5.8
1.9
CH4
27.8
42.8
41.3
CnHm
2.1
2.4
CO2
39.6
34.5
33.8 N2
4.7
Heat 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 %.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

16. 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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

17. Two-stage hydrolysis for ethanol production from plant biomass
Wood
Hydrolysis by 70 % H2SO4 and inversion
Pre-hydrolyzed wood
Pre-hydrolysis 2 % HCl
Hydrolyzate
C5 – sugars
Ethanol
Fermentation
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
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 % the yield of ethanol.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

18. Scheme of ethanol production from wood
Wood sawdust
Catalytic fractionation of main components or explosive autohydrolysis
Products from hemicelluloses and amorphous cellulose
Cellulose
Low molecular mass lignin
Catalytic hydrolysis
Fermentation
Solution of glucose
Ethanol
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
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

19. Hydrocarbons motor fuels from lignocellulosic biomass
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

20. Phenolic Intermediates
Multistep scheme of lignin hydroliquifaction to green fuels and oxygenates
Lignin
Phenolic Intermediates
Naphthenic
fuel additive
Aromatic fuel additive
Oxygenate
Base Catalyzed Depolymerization
(BCD)
Hydrodeoxygenation
(HDO)
Selective Hydrogenolysis
(HT)
Etherification
Hydrocracking
(HCR)
Selective Ring
Hydrogenation
(SRH)
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21. Biomass liquefaction without expensive hydrogen application
Pyrolysis by metallic iron, promoted by Na2CO3:
Metallic iron regeneration:
Yield of liquid products 14% mas. B i o m a s 4 - 6 C F e O +
Oil product Fe
Lignin catalytic liquefaction in methanol:
Proposed mechanism of liquefaction:
Yield of liquid hydrocarbons % mas.
Liquefaction by melted alkali formate:
The highest yield of oil (16.4 % mas.) was observed at 400 °C B i o m a s +
Melted alkali 3 - 4 5 C O l p r d u c t
Wood biomass liquefaction by melted formate/alkali mixtures and with the use of metallic iron/Na2CO3 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.
Kuznetsov B.N. Int. J. of Hydrogen Energy (2009)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

22. Liquefaction of wood/plastics mixtures
Polyolefines 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.
Influence of polymer nature on the yield of liquid products of beech/polyolefine (1:1) mixture pyrolysis at 400 °C 5 10 15 20 25
iPP
aPP PE
% wt. 1 2
Influence of biomass origin on the yield of liquid products of biomass/aPP (1:1) pyrolysis at 400 °C
Light liquid
Heavy
liquid 30 35
Cellulose
Beech
wood
Pine
Hydrolytic
lignin
Yield, % wt.
(1 – fraction < 180 °C, 2- fraction > 180 °C)
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

23. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

24. 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
1.6 HY 56
33.2
17.5
1.8
Si/Al-30 62
25.1
31.8
2.3
Si/Al-100 49
22.2
21.7
2.0
350 53
30.9
16.0
3.2
30.7
25.2
3.8 71
44.3
20.6
4.9 64
35.0
22.9
4.5
400
27.4
9.2
4.1
26.7
14.2
5.3 55
28.6
14.0
5.8
26.8
13.9
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

25. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Composition of liquid products of lignin conversion in ethanol over zeolite catalysts at 400 °C (CMS data)
Products
Content, %
Without catalyst НУ
HSZ-30
HSZ-100
Alkanes, alkenes
<0,1
0,1
0,2
15,2
Acids, aldehydes, ketones, acetals
4,9
8,4
3,2
1,4
Esters
5,5
3,9
14,8
2,1
Aliphatic alcohols
9,9
20,9
16,1
10,0
1,1-diethoxyethane
1,2
41,7
59,1
51,3
Benzene derivatives
5,8
6,0
1,8
2,4
Phenol 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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

26. 4. Chemicals from wood biomass
Lignin is non-regular polymer composed of phenylpropane fragments
Main components of wood biomass
Cellulose (C6H10O5)n – %
Hemicellulose (C5H8O4)n – %
Lignin – %
Extractive compounds – %
Cellulose is a linear polymer, constructed from C6-units
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27. Scheme of cellulose transformation in the presence of acid catalysts
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

28. Chemical products from glucose
J. N. Chheda, G. W. Huber, J. A. Dumesic, Angew. Chem. Int. Ed., 2007
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29. Chemical and fuels from levulinic acid
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30. Formation of acid groups SO3H and COOH in catalysts
Influence of catalyst nature on the conversion of cellulose in hydrolysis at 150 °C
Catalyst
Treatment
SBA-15
Mercaptotrimetoxysilane +H2O2
Sibunit
H2SO4 + K2Cr2O7
H2SO4
TEG (thermally expanded graphite)
Proposed structure of carbon catalyst with –SO3H, –COOH and –OH groups*
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.
* Satoshi Suganuma et.al. JACS
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

31. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Influence of catalyst nature on the yield of glucose in cellulose hydrolysis at 150 °C (12 h) (catalyst/cellulose wt. ratio = 1)
1 – cellulose conversion, 2 – glucose yield
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

32. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
Kinetic curves of levulinic acid (LA) formation from different substrates at 98 °C in the presence of HCl (3.8 M)
1 – sucrose, 2 – fructose, 3 – glucose, 4 – abies wood, 5 – aspen wood, 6 – cellulose
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.
Taraban’ko V.E., Chernyak M.Yu., Aralova S.V., Kuznetsov B.N. React. Kinet. Catal. Lett. (2002)
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33. "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
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

34. Products of lignin catalytic transformations
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
Acetylene, ethylene
Phenolic
acids,
catechol
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35. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Catalytic and non-catalytic oxidation of wood lignins to vanillin and syringaldehyde
Used lignin
Oxidation reagent
Catalyst
Yield, % mas. to lignin
Vanillin
Syringaldehyde
Fir wood
Nitrobenzene -
27.5
Air
11.4
Aspen wood
12.9
30.7 O2
4.8
7.7
Antraquinone
6.4
14.6
CuO 11 30
Softwood sulphite lignin
16.5
Softwood sulphite lignin (Syas Plant
Cu(OH)2
14.2
Softwood sulphite lignin (Monsano) Cu 10
Hardwood sulphite lignin
6.1
10.1
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
Kuznetsov B.N., Kuznetsova S.A., Danilov V.G., Tarabanko V.E. Chem. Sustain. Dev. (2005)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

36. Process characteristics
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
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37. 6. Integrated processing of lignocellulosic biomass
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

38. Carbohydrates and lignosellulosic materials
Biorefinery scheme described in the Biomass program of US Department of Energy
Carbohydrates and lignosellulosic materials
Pyrolysis/gasification
Hydrolysis(enzymatic and chemical)
Syngas
Bio-oil
Fermentation
Hydrogen
Fuels
Ethanol
Platform molecules
Energy
Chemicals
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

39. Scheme of integrated catalytic conversion of wood to liquid biofuels
Wood biomass
Catalytic oxidative fractionation
Soluble lignin
Cellulose
Catalytic conversion
Liquid hydrocarbons
Catalytic hydrolysis
Glucose
Bioethanol
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

40. Influence of temperature on cellulosic product yield and composition.
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, °C
Yield 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
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41. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
SEM images of samples MCC “Vivapur” (А) and cellulose obtained from aspen- wood with TiO2 (B) catalyst A B
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

42. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
Glucose
Levulinic
acid
Modified
cellulose
Wood
composites
Bioethanol
Biodegradable
polymers
Solid biofuels
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

43. Integrated processing of birch-wood to chemical products
Yield of chemical products at integrated processing of birch wood
Product
C5-sugars
Microcrystalline cellulose
Vanillin
Syringaldehyde
Levulinic acid
Phenolic substances
Yield, % mas.
20.0
32.5
1.4
3.1
10.5
9.5
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

44. Integrated processing of larch-wood to chemical products
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
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
Kuznetsov B.N., Kuznetsova S.A., Tarabanko V.E. Russian Chem. J. (2004)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

45. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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 .
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013

46. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
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47. Thank you for your attention!
Suburb of Krasnoyarsk
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