advanced catalytic processes in biorefinary of lignocellulosic biomass
DESCRIPTION
Siberian Federal University. Institute of Chemistry and Chemical Technology SB RAS. Advanced catalytic processes in biorefinary of lignocellulosic biomass. B.N. Kuznetsov Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia - PowerPoint PPT PresentationTRANSCRIPT
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.
"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 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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Scheme of autothermal carbonization of biomass in a fluidized bed of oxidation catalyst
Powdery biomass
Air
Gas Char
Fluidized
bed of
catalyst
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
* 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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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 %.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
4. Liquid fuels from wood biomass
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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.
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Chemical products from glucose
J. N. Chheda, G. W. Huber, J. A. Dumesic, Angew. Chem. Int. Ed., 2007
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
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0,7
0,8
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Time, min
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nce
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f L
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5
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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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
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30
40
50
5 15 25 35
Time, min
Ye
ld, %
on
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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)
"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 6. Integrated processing of lignocellulosic biomasslignocellulosic biomass
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Scheme of integrated catalytic conversion of wood to liquid biofuels
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
0
200
400
600
800
1000
1200
1400
0 10 20 30 40 50 60
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nsit
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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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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)
"Международное сотрудничество в сфере биоэнергетики", Москва, 2013
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 .
"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
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"Международное сотрудничество в сфере биоэнергетики", Москва, 2013