Presentation on theme: "Advanced catalytic processes in biorefinary of lignocellulosic biomass B.N. Kuznetsov Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk,"— Presentation transcript:
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 Institute of Chemistry and Chemical Technology SB RAS Siberian Federal University
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. CHNSOCelluloseLigninHemicelluloses Pine wood 184.108.40.206.245.848.229.415.3 Aspen wood 220.127.116.11.146.146.321.824.5 Beech wood 45.96.00.2 47.746.425.322.4 Spruce wood 18.104.22.168.143.250.327.715.4 a 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
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 GasificationPyrolysis Hydrolysis Fermentation Extraction Etherification Liquid fuels Gaseous fuels Solid Liquid Gaseous Fuels Biodiesel Ethanol Butanol
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 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 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 123456789 Quartz sand Al-Cu-Cr oxide catalyst Flow rate of gases (m 3 / h) 95.194.8100.3108.9110.3110.9111.0109.9153.8 Composition of reaction mixture Lignin (kg/m 3 ) 0.320.322.214.171.124.180.250.410.12 Oxygen (% vol) 13.7126.96.36.199.86.58.811.56.9 Water/steam (% vol) 34.836.121.936.221.933.732.745.435.3 Carbon dioxide (% vol) --188.8.131.52.53.8-4.3 Temperature of bed ( O C) 770820760785770800780670815 Yield, kg/kg 0.180.200.160.184.108.40.206.280.21 Properties of char products obtained by lignin carbonization in a fluidized bed of catalyst Indices Experiment number 123456789 Quartz sand Al-Cu-Cr oxide catalyst Porosity (cm 3 /g) 1.621.791.581.731.881.711.721.812.15 Surface area (m 2 /g) 126472110-144-2286 Ash content (%) 18.216.721.117.421.516.213.512.116.1 Ash content in fraction of particles > 0.2 mm (%) 220.127.116.11.818.104.22.168.58.3 I 2 sorption ability (%) 6253342334330738 "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 "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Char material Temperature, °С H 2 content, % vol. Tar content, g/nm 3 Heat of combustion, MJ/nm 3 From lignite670-75050-60следы10,5-11,1 From birch wood620-71058-651,010,2-10,8 From hydrolysis lignin 670-78052-59следы10,2-10,5 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 H 2 content 60-65 % vol. and very low amount of tar impurities. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013 * Literature data
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
Catalytic activity of metallurgical slags materials in reaction of methanization of the mixture CO + H 2 + H 2 O: 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 1.71.2 Temperature in the upper bed of slag, °C650655660 Yield of dry gas, m 3 /kg sawdust0.680.580.60 Composition of dry gas, % wt. H2H2 22.317.916.4 CO22.214.171.124 CH 4 27.842.841.3 CnHmCnHm 126.96.36.199 CO 2 39.634.533.8 N2N2 188.8.131.52 Heat of combustion of dry gas, kJ/nm 3 141501860017800 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 hydrolysis Two-stage hydrolysis C 6 -sugarsC 5 -sugarsC 6 -sugarsC 5 -sugars Aspen wood49.418.843.8-19.926.8 Wheat straw37.314.235.1-14.821.4 C 5 -sugars removal at the pre-hydrolysis stage increases on 30-35 % the yield of ethanol. Wood Hydrolysis by 70 % H 2 SO 4 and inversion Pre-hydrolysis 2 % HCl Hydrolyzate C 5 – sugars Pre-hydrolyzed wood Ethanol Fermentation "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 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 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
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 Naphthenic fuel additive Aromatic fuel additive Oxygenate fuel additive Base Catalyzed Depolymerization (BCD) Hydrodeoxygenation (HDO) Hydrodeoxygenation (HDO) Selective Hydrogenolysis (HT) Etherification Hydrocracking (HCR) Selective Ring Hydrogenation (SRH) "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Biomass liquefaction without expensive hydrogen application Lignin catalytic liquefaction in methanol: Proposed mechanism of liquefaction: Yield of liquid hydrocarbons 40-45 % mas. Wood biomass liquefaction by melted formate/alkali mixtures and with the use of metallic iron/Na 2 CO 3 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 Na 2 CO 3 : Metallic iron regeneration: Yield of liquid products 14% mas. Biomass 400-600 °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 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. 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 iPPaPPPE % wt. 1 2 1 2 1 2 Influence of biomass origin on the yield of liquid products of biomass/aPP (1:1) pyrolysis at 400 °C Light liquid Heavyliquid 0 5 10 15 20 25 30 35 Cellulose Beech wood Pine wood Hydrolytic lignin Yield, % wt. (1 – fraction 180 °C) "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 C 5 -C 13 hyrocarbons According to GC-MS data the light liquids of biomass/plastic hydropyrolysis contain mainly normal paraffines C 7 -C 13 (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 Zeolite catalysts in H-form Conversion, % wt. Yield of products soluble in ethanol, % wt. Yield* of gaseous products, % wt. < 180 °C> 180 °C 300 absent5030.113.11.6 HY56184.108.40.206 Si/Al-306220.127.116.11 Si/Al-1004918.104.22.168 350 absent5330.916.03.2 HY6230.725.23.8 Si/Al-307144.320.64.9 Si/Al-1006435.022.94.5 400 absent4922.214.171.124 HY5326.714.25.3 Si/Al-305528.614.05.8 Si/Al-1005326.813.94.9 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) Products Content, % Without catalyst НУHSZ-30HSZ-100 Alkanes, alkenes <0,10,10,215,2 Acids, aldehydes, ketones, acetals 4,98,43,21,4 Esters 5,53,914,82,1 Aliphatic alcohols 9,920,916,110,0 1,1-diethoxyethane 1,241,759,151,3 Benzene derivatives 5,86,01,82,4 Phenol and its derivatives 72,719,04,515,4 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 (C 6 H 10 O 5 ) n – 40-50 % Hemicellulose (C 5 H 8 O 4 ) n – 15-30 % Lignin– 16-33 % Extractive compounds– 1-10 % Lignin is non-regular polymer composed of phenylpropane fragments Cellulose is a linear polymer, constructed from C 6 -units "Международное сотрудничество в сфере биоэнергетики", Москва, 2013 4. Chemicals from wood biomass
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
Chemical and fuels from levulinic acid "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Formation of acid groups SO 3 H and COOH in catalysts CatalystTreatment SBA-15 Mercaptotrimetoxysilane +H 2 O 2 Sibunit H 2 SO 4 + K 2 Cr 2 O 7 Sibunit H 2 SO 4 TEG (thermally expanded graphite) H 2 SO 4 "Международное сотрудничество в сфере биоэнергетики", Москва, 2013 Proposed structure of carbon catalyst with –SO 3 H, –COOH and –OH groups* * Satoshi Suganuma et.al. JACS. 2008. The catalytic activity of carbon with SO 3 H, 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. 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. 1 – sucrose, 2 – fructose, 3 – glucose, 4 – abies wood, 5 – aspen wood, 6 – cellulose Effect of the catalyst nature on the yield of levulinic acid from glucose at 98 °C and a Hammet acidity function of H o = -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 H 2 SO 4 Fe 2 (SO 4 ) 3 Al 2 (SO 4 ) 3 150200250150200250150200250150200250 Yield of levulinic acid, % wt. --0.6-22.125.2-1.84.7-16.618.4 Degree of the cellulose conversion, % 0.014.523.821.762.6126.96.36.1992.96.458.158.6 Yield of levulinic acid in thermocatalytic transformations of wood by steam in the presence of 5 % of H 2 SO 4, % wt. Temperature, °CBeechAspenPineSpruce 20016.415.614.513.3 24017.315.715.514.5 "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 Catalytic and non-catalytic oxidation of wood lignins to vanillin and syringaldehyde Used lignin Oxidation reagent Catalyst Yield, % mas. to lignin VanillinSyringaldehyde Fir woodNitrobenzene-27.5- Fir woodAir-11.4- Aspen wood Nitrobenzene-12.930.7 Aspen wood O2O2 -4.87.7 Aspen wood Antraquinone6.414.6 Aspen wood O2O2 CuO1130 Softwood sulphite lignin Nitrobenzene-16.5- Softwood sulphite lignin (Syas Plant Air-3.5-4.5- Softwood sulphite lignin (Syas Plant O2O2 Cu(OH) 2 14.2- Softwood sulphite lignin (Monsano) O2O2 Cu10- Hardwood sulphite lignin Nitrobenzene-6.110.1 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 0,2-0,33 Vanillin concentration, g/l 9-127-8 Lignosulphonates expenses, kg/kg vanilline 15-2038 Coefficient of vanillin distribution at the extraction stage 10-156 Time of vanillin extraction, h 0,5-0,630 "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
6. Integrated processing of lignocellulosic biomass "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Carbohydrates and lignosellulosic materials Pyrolysis/gasificationHydrolysis(enzymatic and chemical) SyngasBio-oil Fermentation HydrogenFuelsEthanolPlatform 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 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.
Influence of aspen-wood delignification temperature on residual lignin content in cellulosic product (reaction conditions: H 2 O 2 5 % wt., CH 3 COOH 25 % wt., catalyst TiO 2 1 % wt., LWR 15) "Международное сотрудничество в сфере биоэнергетики", Москва, 2013 Influence of temperature on cellulosic product yield and composition. Delignification conditions: CH 3 COOH – 25 % mas., H 2 O 2 – 4 % mas., LWR 10, time 4 h, 1 % wt. TiO 2 Temperature, °C Yield of cellulosic product, % * Composition of product, % ** cellulosehemicelluloses lignin 7076.775.18.3 15.6 8072.884.38.0 6.3 9060.890.37.7 1.3 10050.291.17.4 0.6
SEM images of samples MCC “Vivapur” (А) and cellulose obtained from aspen- wood with TiO 2 (B) catalyst A B "Международное сотрудничество в сфере биоэнергетики", Москва, 2013 Diffraction patterns of cellulose from aspen wood obtained with H 2 SO 4 (1), TiO 2 (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 Lignocellulosicbiomass Separation LigninNanoporous carbons Cellulose Liquid hydrocarbons SorbentsBinding agents GlucoseLevulinic acid Modified cellulose Wood composites BioethanolBiodegradable polymers Solid biofuels "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Integrated processing of birch-wood to chemical products Yield of chemical products at integrated processing of birch wood ProductC 5 -sugars Microcrystalline cellulose VanillinSyringaldehydeLevulinic acid Phenolic substances Yield, % mas. 20.032.51.43.110.59.5 "Международное сотрудничество в сфере биоэнергетики", Москва, 2013
Yield of chemical products at integrated processing of larch wood Product ArabinogalactanDihydroquercetinMicrocrystalline cellulose VanillinLevulinic acid Phenolic substances Yield, % mas.18,10,631,25,48,611,9 Larch wood Extraction by water at 100 о С Extracted wood Dihydroquercetin Arabinigalactan Catalytic oxidation by О 2 at 170 °С Catalytic delignification by H 2 O 2 at 130 °С Levulinic acid CelluloseVanillin 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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