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
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
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
Characteristics of the siberian wood species
Type of
wood
Elemental composition,
% wt.a
Chemical composition, % wt.
C
H
N
S
O
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
15.4
a
Cellulose Lignin
Dry ash-free basis
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Hemicelluloses
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
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:
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Processes of plant biomass conversion to the more usable
energy forms
Plant biomass
Thermal
liquefaction
Gasification
Pyrolysis
Hydrolysis
Fermentation
Liquid fuels
Gaseous
fuels
Solid
Liquid
Gaseous
Fuels
Ethanol
Butanol
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Extraction
Etherification
Biodiesel
3. Gaseous and solid fuels from
wood biomass
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Scheme of autothermal carbonization of biomass in a
fluidized bed of oxidation catalyst
Gas
The main steps of biomass oxidative
carbonization in fluidized bed of catalyst
Char
Product cooling
Fluidized
Char combustion
and gasification
bed of
Char formation
catalyst
Volatiles
evolution and
oxidation by
catalyst
Biomass heating
Powdery
biomass
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
Air
Volatile
compounds
oxidation by the
catalyst
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Heat
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 fluidizedbed 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
Parameters of thermal treatments of lignin in fluidized bed of oxidation catalyst and yields of char
Experiment number
1
Parameter of the process
2
3
Quartz
sand
Flow rate of gases (m3 / h)
4
5
6
7
8
9
Al-Cu-Cr oxide catalyst
95.1
94.8
100.3
108.9
110.3
110.9
111.0
109.9
153.8
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
-
-
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
Composition of reaction mixture
Carbon dioxide (% vol)
Properties of char products obtained by lignin carbonization in a fluidized bed of catalyst
Experiment number
1
Indices
2
3
4
Quartz
sand
Porosity (cm3 /g)
5
6
7
8
9
Al-Cu-Cr oxide catalyst
1.62
1.79
1.58
1.73
1.88
1.71
1.72
1.81
2.15
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
6
25
33
42
33
43
30
7
38
Surface area (m2 /g)
I2 sorption ability (%)
"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
850-900 °C
Fuel gas
particles up to 70-90 % energy
demanded for autothermal
regime of gasification process
Char
Pyrolysis
reactor
Fluidized bed
of catalyst
700-750 °C
Gasification
reactor
Recirculated
particles
Steam
Air
Syn-gas
CO+H2
Biomass
• Significant decrease of the
consumption of expensive
oxygen
• Low concentration of tar in
produced syn-gas; this facilitate
Oxygen
its purification and increases the
process ecological safety
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Gasification of char materials by water-steam in fluidized bed
of Martin slag
Temperature,
°С
H2 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
670-780
52-59
следы
10,2-10,5
650-780*
35-57*
20-70*
11,8-13,8*
Char material
From hydrolysis
lignin
Wood and
agricultural
wastes
* Literature data
Steam gasification of char produces gas with H2 content 60-65 % vol. and very low
amount of tar impurities.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Scheme of methane production by wood gasification in
fluidized bed of methanization catalyst
Methan-containing
5 gas
Wood sawdust
А
2
1
6
Smoke gases
3
8
7
9
air
4
steam
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
100
Catalytic activity of metallurgical slags
materials in reaction of methanization of
the mixture CO + H2 + H2O:
Activity, %
80
60
40
20
0
1
2
3
Samples
4
5
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
Birch sawdust in bed of Birch sawdust in bed of Aspen sawdust in bed
quartz sand
activated Martin slag
of activated Martin slag
Indices
Steam consumption (420°С) kg/kg
sawdust
Temperature in the upper bed of slag, °C
Yield of dry gas, m3/kg sawdust
Composition of dry gas, % wt.
H2
CO
CH4
CnHm
CO2
N2
Heat of combustion of dry gas, kJ/nm3
1.7
1.2
1.2
650
0.68
655
0.58
660
0.60
22.3
5.8
27.8
2.1
39.6
2.4
14150
17.9
1.2
42.8
2.4
34.5
1.2
18600
16.4
1.9
41.3
1.9
33.8
4.7
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
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
Two-stage hydrolysis for ethanol production from plant biomass
Wood
Hydrolysis by 70 %
H2SO4 and inversion
Pre-hydrolyzed
wood
Hydrolyzate
Pre-hydrolysis
2 % HCl
C5 – sugars
Fermentation
Ethanol
Influence of composition of the hydrolyzates on the yield of ethanol
Composition of hydrolyzate, %
Biomass type
One-stage
hydrolysis
Two-stage
hydrolysis
Ethanol yield, % wt.
One-stage
hydrolysis
Two-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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
Solution of glucose
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
Fermentation
Ethanol
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
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
Multistep scheme of lignin hydroliquifaction to green fuels
and oxygenates
Lignin
Base Catalyzed
Depolymerization
(BCD)
Phenolic
Intermediates
Hydrodeoxygenation
(HDO)
Selective Ring
Hydrogenation
(SRH)
Hydrodeoxygenation
(HDO)
Hydrocracking
(HCR)
Aromatic
fuel additive
Selective
Hydrogenolysis
(HT)
Etherification
Oxygenate
fuel additive
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Naphthenic
fuel additive
Biomass liquefaction without expensive hydrogen application
Pyrolysis by metallic iron, promoted by
Na2CO3:
Biomass
Fe
FeO + C + Oil product
400-600 °C
Metallic iron regeneration:
FeO + C
0.1MPa
600 °C
Lignin catalytic liquefaction in methanol:
Lignin + Methanol
Liquids
Proposed mechanism of liquefaction:
Fe + CO
Yield of liquid products 14% mas.
CH3OH + H2O
Lignin + H2
Liquefaction by melted alkali formate:
Biomass + Melted alkali
Fe-Zn-Cr
380-410 °C
300-450 °C
Oil product
Fe-Zn-Cr
3H2 + CO2
Product - Ar - H
Product-Ar-H + CH3OH
Product-Ar-CH3 + H2O
Yield of liquid hydrocarbons 40-45 % mas.
The highest yield of oil (16.4 % mas.)
was observed at 400 °C
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
Liquefaction of wood/plastics mixtures
Polyolefines contain rather high amount of hydrogen and they provide hydrogen at thermal coprocessing 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 biomass origin on the yield
of liquid products of biomass/aPP (1:1)
pyrolysis at 400 °C
Influence of polymer nature on the yield
of liquid products of beech/polyolefine
(1:1) mixture pyrolysis at 400 °C
25
20
30
% wt.
Yield, % wt.
35
25
20
15
10
15
2
2
1
1
1
2
10
5
5
0
Cellulose
Beech
wood
Pine
wood
Heavy liquid
Light liquid
Hydrolytic
lignin
0
iPP
aPP
PE
(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
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
16
30
25
1
1
25
А
35
B
20
12
30
5
20
10
25
15
6
4
% mas.
8
% mas.
15
5
20
10
4
2 3
5
2
0
0
6
7
8
9
10
11
Number of carbon atoms in the molecule
12
13
15
2
10
3
5
% mas.
14
% mas.
40
10
4
5
0
0
5
6
7
8
9
10
11
12
Number of carbon atoms in the molecule
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
Lignin catalytic depolymerization in ethanol medium over
acid zeolite catalysts
Temperature, °C
300
350
400
Zeolite catalysts
in H-form
Conversion,
% wt.
absent
HY
Si/Al-30
Si/Al-100
absent
HY
Si/Al-30
Si/Al-100
absent
HY
Si/Al-30
Si/Al-100
50
56
62
49
53
62
71
64
49
53
55
53
Yield of products soluble in
ethanol, % wt.
< 180 °C
> 180 °C
30.1
33.2
25.1
22.2
30.9
30.7
44.3
35.0
27.4
26.7
28.6
26.8
13.1
17.5
31.8
21.7
16.0
25.2
20.6
22.9
9.2
14.2
14.0
13.9
Yield* of gaseous
products, % wt.
1.6
1.8
2.3
2.0
3.2
3.8
4.9
4.5
4.1
5.3
5.8
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Composition of liquid products of lignin conversion in
ethanol over zeolite catalysts at 400 °C (CMS data)
Content, %
Products
Alkanes, alkenes
Acids, aldehydes,
ketones, acetals
Esters
Aliphatic alcohols
1,1-diethoxyethane
Benzene derivatives
Phenol and its
derivatives
Without
catalyst
<0,1
НУ
HSZ-30
HSZ-100
0,1
0,2
15,2
4,9
8,4
3,2
1,4
5,5
9,9
1,2
5,8
3,9
20,9
41,7
6,0
14,8
16,1
59,1
1,8
2,1
10,0
51,3
2,4
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
4. Chemicals from wood biomass
Lignin is non-regular
polymer composed of
phenylpropane fragments
Main components of wood biomass
– 40-50 %
Cellulose (C6H10O5)n
Hemicellulose (C5H8O4)n – 15-30 %
CHO
H-C-H
– 16-33 %
Lignin
H-C-H
Extractive compounds – 1-10 %
HOH 2C
OMe
HC - O
CH 2OH
HC
- Ar - O - C - H
CH 2OH
Cellulose is a linear polymer, constructed
from C6-units
H
HO OH
H
CH 2 OH
OH
H
H
H
H
O
OH
OH
H
OH
O
H
MeO
O - CH 2
H
H
H
HC
H
HC
O
H
OH
OH H
H
HOH 2C
O
H
OH
CH 2 OH
HC
CH 2 OH
O
O
H
O
CH 2 OH
H
HC - O
H
CH 2
OH
H(C 6 H 10 O5 )n-O-CH
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
OMe
O
OMe
OH
Scheme of cellulose transformation in the presence of acid
catalysts
CH2OH
H
O
CH2OH
H C
O
H
H
OH
H
OH
O
OH
OH H
H
H
O
2
HO
H
H
O
H
n
H OH
Glucose
Cellulose
Levoglucosenone
O
O
C-H
HOH2C
H
Hydroxymethylfurfural
CH3 - C - CH2 - CH2 - C - OH
O
O
Levulinic acid
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Chemical products from glucose
O
FumaricAcid
O
Aspartic Acid
OH
O
amination
OH
HO
Malic Acid
O
OH
fer
me
n ta
HO
O
fermentation
Krebs Pathway
tio
n
OH
2,5-Furandicarboxylic acid
oxidation
OH
O
Glucose
NH2
O
fermentation
OH
OH
O
O
dehydration
HO
Aspartic Acid O
HO
on
ati
t
n
me
fer
O
OH
HO
O
O
OH
dehydration
HO
O
Itaconic acid
O
O
O
Succinic Acid
3-Hydroxypropionic acid
NH2
O
HO
OH
HO
O
O
HO
O
OH
HO
OH
t
en
m
r
fe
O
io
at
OH
ox
id
OH
ati
on
OH
n
hydrogenation
HO
OH
OH
O ox
ida
tio
Gluconic Acid
n
O
HO
OH
OH
OH
fermentation&
oxidation
O
Levulinic Acid O
5-Hydroxymethylfurfural
OH
O
OH
OH
OH
OH
OH
HO
3-Hydroxybutyrolactone
OH
HO
HO
Glutamic Acid NH2
O
OH
OH
Sorbitol
J. N. Chheda, G. W. Huber, J. A. Dumesic, Angew. Chem. Int. Ed., 2007
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
OH
Glucaric Acid
O
Chemical and fuels from levulinic acid
H3C
H3C
O
O
O
CH3

5-nonanone
-valerolactone
Tetrehydrofuran
SOLVENTS
FUELS
O
H3C
O
O
H3C
2-methyl-tetrahydrofuran
O
Ethyl levulinate
CHEMICAL INTERMEDIATES
OH
PLASTICISERS
RESINS
HO
1,4-butanediol
O
Levulinic Acid
OH
CH2
Acrylic acid
O

R

R

HO

 C
O
O
-angelicalactone

HO

H3C
FOOD, FLAVOURING AND
FRAGRANCE COMPONENTS
O
HO
Succinic Acid O
CH3

H3C
1,4-pentanediol
Diphenolic acid
ANTI-FREEZE AGENTS
O
H3C
PHARMACEUTICAL
AGENTS
Na
HO
O
5-bromolevulinic acid
Br
POLYMERS
O
O
O
O
O
sodium levulinate
HERBICIDES
O
HO
NH
NH
OH
O
-aminolevulinic acid
O
n
Nylon 6,6 (polyamide)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Formation of acid groups SO3H and COOH
in catalysts
Catalyst
SBA-15
Sibunit
Sibunit
TEG (thermally
expanded graphite)
Influence of catalyst nature on the conversion
of cellulose in hydrolysis at 150 °C
Treatment
Mercaptotrimetoxysilane +H2O2
H2SO4 + K2Cr2O7
H2SO4
H2SO4
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.
* 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.
Chemical and combined treatments of
MCC increase its conversion in catalytic
hydrolysis.
"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)
90
1
1
1 – cellulose conversion,
2 – glucose yield
70
Glucose yield, % wt.
Cellulose conversion, % wt.
80
60
50
1
40
2
20
0
1
2
1
30
10
2
2
1
2
1
2
2
Without catalyst
SBA-15 twostage synthesis
SBA-15 onestage synthesis
TEG + H2SO4
Sibunit
Sibunit H2SO4
K2Cr2O7+H2SO4
Nafion N551PW
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
Levulinic acid yield, % mol.
35
30
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
25
20
15
10
5
0
Н3PO4
Н2SO4
НCl
Kinetic curves of levulinic acid (LA) formation from different substrates at 98 °C in
the presence of HCl (3.8 M)
100
4
0,7
80
2
60
3
40
20
Concentration of LA, g/l
Yield of LA, mol. %
0,8
1
0,6
0,5
5
0,4
6
0,3
0,2
0,1
0
0
100
200
Time, min
300
0
0
100
200
300
Time, min
400
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)
"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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Products of lignin catalytic transformations
Acetic acid, phenol,
substituted phenols, CO,
methane
Acetylene, ethylene
Phenols, cresols,
substituted phenols
pyrolysis
fast
thermolysis
hydrogenation
Phenol,
substituted
phenols
hydrolysis
Phenolic
acids,
catechol
alcali fusion
oxidative
Vanilin,
demethylsulfide, methyl
mercaptan, dimethyl
sulfoxide
enzymatic
oxidation
microbial
conversions
Lignin with increased
level of polymerization
Oxidized lignin
for paints and
coatings
Vanilic, ferulic, coumaric
and other acids
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Catalytic and non-catalytic oxidation of wood
lignins to vanillin and syringaldehyde
Yield, % mas. to lignin
Catalyst
Fir wood
Nitrobenzene
Fir wood
Vanillin
Syringaldehyde
-
27.5
-
Air
-
11.4
-
Aspen
wood
Nitrobenzene
-
12.9
30.7
Aspen
wood
O2
-
4.8
7.7
Antraquinone
6.4
14.6
O2
CuO
11
30
Nitrobenzene
-
16.5
-
Aspen
wood
Aspen
wood
Softwood
sulphite
lignin
Softwood
sulphite
lignin
(Syas Plant
Softwood
sulphite
lignin
(Syas Plant
Air
-
3.5-4.5
Yield of aromatic aldehydes at birch wood
oxidation by molecular oxygen at 170 °C
in the presence of Cu(OH)2 catalyst
50
40
Yeld, % on lignin
Oxidation
reagent
Used lignin
30
20
1
10
2
-
3
0
5
O2
Cu(OH)2
14.2
15
25
35
Time, min
-
1– total yield, 2 – syringaldehyde, 3 - vanillin
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
6. Integrated processing of
lignocellulosic biomass
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Biorefinery scheme described in the Biomass
program of US Department of Energy
Carbohydrates and lignosellulosic materials
Pyrolysis/gasification
Hydrolysis(enzymatic and chemical)
Fermentation
Syngas
Hydrogen
Bio-oil
Fuels
Energy
Ethanol
Platform molecules
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
Scheme of integrated catalytic conversion of wood to liquid biofuels
Wood biomass
Catalytic oxidative fractionation
Soluble lignin
Catalytic conversion
Bioethanol
Cellulose
Catalytic hydrolysis
Glucose
Liquid hydrocarbons
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
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
Composition of product, % **
cellulose
hemicelluloses
Temperature, °C
Yield of cellulosic
product, %*
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
lignin
SEM images of samples MCC “Vivapur” (А) and cellulose obtained from
aspen- wood with TiO2 (B) catalyst
B
A
Diffraction patterns of cellulose from aspen wood obtained with H2SO4 (1), TiO2 (2) catalyst
and industrial microcrystalline cellulose Vivapur (3)
1400
1200
1
Intensity
1000
2
3
2
800
1
600
3
400
200
0
0
10
20
30
40
50
60
2 Theta
According to SEM, FTIR and XRD data the structure of wood cellulose corresponds to microcrystalline cellulose.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Scheme of integrated conversion of lignocellulosic biomass
into chemicals functional materials and biofuels
Lignocellulosic biomass
Separation
Lignin
Liquid
hydrocarbons
Sorbents
Solid
biofuels
Nanoporous
carbons
Binding
agents
Wood
composites
Cellulose
Modified
cellulose
Levulinic
acid
Biodegradable
polymers
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Glucose
Bioethanol
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
Pentosanes
Oxidation by O2 at 170 °C
Xylite
Furfural
Chemically
pure cellulose
Phenolic
substances
Microcrystalline
cellulose
Phenols
Antioxidants
Aromatic
compounds
Cellulose
Vanillin
Syringaldehyde
Levulinic
acid
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
Integrated processing of larch-wood to chemical products
Larch wood
Extraction by water at 100 оС
Arabinigalactan
Dihydroquercetin
Levulinic acid
Extracted wood
Catalytic
delignification by
H2O2 at 130 °С
Catalytic oxidation
by О2 at 170 °С
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
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
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Thank you for your attention!
Suburb of Krasnoyarsk
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013