Advanced catalytic processes in biorefinary of lignocellulosic biomass

1. 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 Siberian Federal University, Krasnoyarsk, Russia

2. Presentation outline 1. Introduction 2. Catalysis in biorefinary 3. Gaseous and solid fuels from wood biomass 4. Liquid fuels from wood biomass 5. Chemicals from wood biomass 6. Integrated processing of wood biomass 7. Conclusive remarks "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

3. 1. Introduction Biomass is an important feedstock for the renewable production of fuels, chemicals, and energy. The worldwide production capabilities for renewable and sustainable biomass production are enormous. In the United States over 370 million dry tons and 1 billion dry tons of annual biomass are obtainable from forest and agricultural lands, respectively. Similarly large biomass production capacity is available in Europe, which could produce 190 million tons of oil equivalent (Mtoe) of biomass with possible increases up to 300 Mtoe by 2030. Russia has around 23 % of world resources of wood and a half of this amount is located in Siberia, therefore in our country the wood biomass is the most suitable resource for bioproducts. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

4. Characteristics of the siberian wood species a Dry ash-free basis "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

5. 2. Catalysis in biorefinary Over the 20th century, the petrochemical and the chemical industry developed numerous catalytic processes to transform hydrocarbon-like compounds into great number of products. However, most of these processes are not suitable for converting biomass. In biorefinery, processing starts from highly oxygenated raw materials, and controlled catalytic de-functionalization is necessary, instead of functionalization used nowadays in the chemical industry. The O/C and H/C molar ratios of fossil and biomass raw materials and of fuels derived from them "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

6. Application of solid catalysts in biomass processing At present the ecology dangerous and corrosive active catalysts on the bases of inorganic acids and alkali solutions are mainly used in biomass conversions. These catalysts should be changed on the more technologically suitable solid acid catalysts and on bifunctional catalysts. • Advantages of the heterogeneous catalysis processes over homogeneous processes : • easy separation of products and catalyst, • less corrosive activity of reaction mixture, • easy regeneration of the catalyst, • better regulation of catalyst performance owing to the wider range of reactions condition. • The next ways are used to increase the efficiency of biomass processing: • Selection of the effective catalysts for polysaccharides conversion. • Using of effective methods of biomass activation and fractionation. • Integration of production of chemicals and biofuels in the combined technological cycle. • This presentation describes the results of study of advanced catalytic processes in biorefinary of wood biomass obtained in the ICCT SB RAS and SFU. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

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

8. 3. Gaseous and solid fuels from wood biomass "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

9. Gas Char Powdery biomass Air 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 Char and gases Powdery biomass Product cooling Char combustion and gasification Char formation Volatiles evolution and oxidation by catalyst Biomass heating Feeding by air through heated fluidized bed of the oxidation catalyst Fluidized bed of catalyst Carbonization and activation of char particles Volatile compounds evolution Volatile compounds oxidation by the catalyst Heat "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

10. Some advantages of the autothermal carbonization process • the process proceeds in autothermal conditions without additional heat supply, resulting in less number of apparatus in technological scheme; • the process productivity is higher in comparison with conventional pyrolysis methods owing to fluidized-bed technology; • the variation of carbon products structure and properties is possible in broad limits; • no pyrolysis tar is formed and gaseous product contain a reduced concentration of harmful compounds. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

11. Parameters of thermal treatments of lignin in fluidized bed of oxidation catalyst and yields of char Properties of char products obtained by lignin carbonization in a fluidized bed of catalyst "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

12. Syn-gas and fuel gas producing from powdery biomass in fluidized bed of catalyst • The advantages of developed process : • Supply by recirculated char particles up to 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 "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

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

14. 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

15. Catalytic activity of metallurgical slags materials in reaction of methanization of the mixture CO + H2 + H2O: 1 – commercial catalyst ANKM-1E, 2 – converter slag, 3 – steel-smelting slag, 4 – Martin slag, 5 – activated Martin slag Influence of conditions of wood sawdust gasification on the yield and composition of produced gases The developed gasification process makes it possible to produce from waste wood the methane-containing gas with calorific value on 30 % higher in comparison with the traditional steam gasification process. Besides, the part of potential heat of the initial raw material, transforming to the potential heat of the produced gas was increased by 10 relative %. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

16. 4. Liquid fuels from wood biomass At the present time, two biomass-derived fuels (so-called first generation of biofuels) have been successfully implemented in the transportation sector: biodiesel (a mixture of long-chain alkyl esters produced by transesterification of vegetable oils with methanol) bioethanol (produced by fermentation of corn and sugar cane-derived sugars). The current biofuel market is largely dominated by ethanol, which accounts for 90% of world biofuel production. Indeed, the rate of ethanol production around the world is increasing rapidly. The urgent task is the development of bioethanol production from non-food lignocellulosic biomass. Wood hydrolyzates of the traditional hydrolysis industry have complex composition and they contain different impurities which inhibits the sugar fermentation process. Different approaches are used to increase the quality of wood hydrolyzates. The key of them should include the preliminary separation of wood on cellulose, hemicelluloses and soluble lignin. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

17. Two-stage hydrolysis for ethanol production from plant biomass Wood Hydrolysis by 70 % H2SO4 and inversion Pre-hydrolyzed wood Pre-hydrolysis 2 % HCl Hydrolyzate C5 – sugars Ethanol Fermentation Influence of composition of the hydrolyzates on the yield of ethanol C5-sugars removal at the pre-hydrolysis stage increases on 30-35 % the yield of ethanol. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

18. Scheme of ethanol production from wood Wood sawdust Catalytic fractionation of main components or explosive autohydrolysis Products from hemicelluloses and amorphous cellulose Cellulose Low molecular mass lignin Catalytic hydrolysis Solution of glucose Fermentation • Conditions of glucose fermentation: • temperature 34 – 36 °C, • amount of yeast 3 – 5 g, • ferment saccharomycescerevisiae, • time of treatment 5 h, • volume of hydrolyzate 0.1 l 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

19. Hydrocarbons motor fuels from lignocellulosic biomass Instead of using biomass to produce oxygenated fuels (such as ethanol) with new compositions, an attractive alternative would be to utilize biomass to generate liquid fuels chemically similar to those being used today derived from oil. These new fuels would be denoted as green gasoline, green diesel and green jet fuel. The most simple way of liquid hydrocarbon producing is the pyrolysis of biomass with following upgrading of bio-oils. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

20. Multistep scheme of lignin hydroliquifaction to green fuels and oxygenates Phenolic Intermediates Lignin Base Catalyzed Depolymerization (BCD) Selective Ring Hydrogenation (SRH) Hydrodeoxygenation (HDO) Hydrodeoxygenation (HDO) Naphthenic fuel additive Hydrocracking (HCR) Aromatic fuel additive Selective Hydrogenolysis (HT) Oxygenate fuel additive Etherification "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

21. B i o m a s s + O i l p r o d u c t Melted alkali 3 0 0 - 4 5 0 ° C Biomass liquefaction without expensive hydrogen application Pyrolysis by metallic iron, promoted by Na2CO3: Lignin catalytic liquefaction in methanol: Fe B i o m a s s F e O + C + Oil product 4 0 0 - 6 0 0 ° C Metallic iron regeneration: Proposed mechanism of liquefaction: Yield of liquid products 14% mas. Liquefaction by melted alkali formate: 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. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013 Kuznetsov B.N. Int. J. of Hydrogen Energy (2009)

22. 35 30 25 20 15 10 5 0 Heavy liquid Beech Light liquid Cellulose Pine Hydrolytic wood wood lignin 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. 25 2 2 1 1 20 1 2 15 % wt. 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 10 5 0 iPP aPP PE Yield, % wt. (1 – fraction < 180 °C, 2- fraction > 180 °C) The highest yield of light hydrocarbons is observed for cellulose, the lowest – for lignin. The influence of biomass nature on the yields of light liquid fraction is more pronounced than that of polyolefin origin. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013 Sharypov V.I., Beregovtsova N.G., Kuznetsov B.N. et. al. J. Sib. Fed. Univ. Chem. 2008)

23. GC-MS data on the distribution of hydrocarbons in the light liquid fraction (b.p. below 180 °C) of mixtures (1:1) pine-wood/polyethylene (A) and pine-wood/polypropylene (B) hydropyrolysis 1 – parafins, 2 – cycloparafins, 3 – olefins, 4 – aromatic compounds, 5 – total contents of C5-C13 hyrocarbons According to GC-MS data the light liquids of biomass/plastic hydropyrolysis contain mainly normal paraffines C7-C13 (about 75 % for pine-wood/PP mixture), alkylbenzenes and alkylfuranes compounds (about 10 %) and non-identified compounds (about 15 %). Sharypov V.I., Beregovtsova N.G., Kuznetsov B.N. et. al. J. Anal. Appl. Pyrolysis (2006) "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

24. Lignin catalytic depolymerization in ethanol medium over acid zeolite catalysts The maximum conversion of lignin (71 % wt.) and the high yield of light fraction (< 180 °C) of liquid products (44 % wt.) were observed at 350 °C in the presence of zeolite catalyst with Si/Al ratio 30. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

25. Composition of liquid products of lignin conversion in ethanol over zeolite catalysts at 400 °C (CMS data) Zeolite catalysts increase significantly (to 50 times) the content of 1,1-diethoxyethane and reduce by 4-16 times of phenol and its derivative in liquid products as compared to non-catalytic process. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

26. Lignin is non-regular polymer composed of phenylpropane fragments Main components of wood biomass Cellulose (C6H10O5)n – 40-50 % Hemicellulose (C5H8O4)n – 15-30 % Lignin – 16-33 % Extractive compounds – 1-10 % Cellulose is a linear polymer, constructed from C6-units 4. Chemicals from wood biomass "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

27. Scheme of cellulose transformation in the presence of acid catalysts "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

28. Chemical products from glucose J. N. Chheda, G. W. Huber, J. A. Dumesic, Angew. Chem. Int. Ed., 2007 "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

29. Chemical and fuels from levulinic acid "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

30. Formation of acid groups SO3H and COOH in catalysts Influence of catalyst nature on the conversion of cellulose in hydrolysis at 150 °C Proposed structure of carbon catalyst with –SO3H, –COOH and –OH groups* Sulfated mesoporous SBA-15 catalyst has the highest activity (cellulose conversion 80 % wt.). It exceeds the activity of acid catalysts Nafion and Amberlyst-15. Chemical and combined treatments of MCC increase its conversion in catalytic hydrolysis. * Satoshi Suganuma et.al. JACS. 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. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

31. Influence of catalyst nature on the yield of glucose in cellulose hydrolysis at 150 °C (12 h) (catalyst/cellulose wt. ratio = 1) 1 – cellulose conversion, 2 – glucose yield HPLС analysis of products of MCC hydrolysis at 150 °C over sulfated SBA-15 catalyst Products of MCC hydrolysis over SBA-15 two-stage synthesis contain mainly glucose. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

32. Effect of the catalyst nature on the yield of levulinic acid from glucose at 98 °C and a Hammet acidity function of Ho = -2.6 Kinetic curves of levulinic acid (LA) formation from different substrates at 98 °C in the presence of HCl (3.8 M) 1 – sucrose, 2 – fructose, 3 – glucose, 4 – abies wood,5 – aspen wood, 6 – cellulose The maximum rates of the LA formation were observed for the fructose and sucrose. Cellulose and wood are less reactive, obviously according to the diffusion limitations during plant polymers hydrolysis. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013 Taraban’ko V.E., Chernyak M.Yu., Aralova S.V., Kuznetsov B.N. React. Kinet. Catal. Lett. (2002)

33. Yield of levulinic acid in thermocatalytic transformations of cellulose by steam Yield of levulinic acid in thermocatalytic transformations of wood by steam in the presence of 5 % of H2SO4, % wt. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

34. Products of lignin catalytic transformations Acetic acid, phenol, substituted phenols, CO, methane Phenols, cresols, substituted phenols Acetylene, ethylene pyrolysis fast thermolysis hydrogenation Phenol, substituted phenols Phenolic acids, catechol hydrolysis alcali fusion oxidative Oxidized lignin for paints and coatings enzymatic oxidation Vanilin, demethylsulfide, methyl mercaptan, dimethyl sulfoxide microbial conversions Lignin with increased level of polymerization Vanilic, ferulic, coumaric and other acids "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

35. Catalytic and non-catalytic oxidation of wood lignins to vanillin and syringaldehyde Yield of aromatic aldehydes at birch wood oxidation by molecular oxygen at 170 °C in the presence of Cu(OH)2 catalyst 1– total yield, 2 – syringaldehyde, 3 - vanillin Kuznetsov B.N., Kuznetsova S.A., Danilov V.G., Tarabanko V.E. Chem. Sustain. Dev. (2005) "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

36. Some characteristics of the developed catalytic process of vanillin producing from lignosulphonates and the industrial technology of Syas Plant "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

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

38. Biorefinery scheme described in the Biomass program of US Department of Energy Carbohydratesand lignosellulosic materials Pyrolysis/gasification Hydrolysis(enzymatic and chemical) Fermentation Syngas Bio-oil Hydrogen Fuels Ethanol Platform molecules Chemicals 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

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

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

41. 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) According to SEM, FTIR and XRD data the structure of wood cellulose corresponds to microcrystalline cellulose. "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

42. Lignocellulosic biomass Separation Lignin Nanoporous Cellulose carbons Liquid Sorbents Binding Modified Levulinic Glucose hydrocarbons agents cellulose acid Biodegradable Bioethanol Wood polymers composites Scheme of integrated conversion of lignocellulosic biomass into chemicals functional materials and biofuels Solid biofuels "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

43. Integrated processing of birch-wood to chemical products Yield of chemical products at integrated processing of birch wood "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

44. Larch wood Extraction by water at 100 оС Extracted wood Arabinigalactan Catalytic delignification by H2O2 at 130 °С Catalytic oxidation by О2at 170 °С Dihydroquercetin Cellulose Vanillin Microcrystalline cellulose Levulinic acid Phenolic substances Integrated processing of larch-wood to chemical products Yield of chemical products at integrated processing of larch wood Kuznetsov B.N., Kuznetsova S.A., Tarabanko V.E. RussianChem. J. (2004) "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

45. 7. Conclusive remarks There are potential analogies between the 20th century petroleum refinery and the 21st century biorefinery. Development of the petroleum refinery took considerable effort to become the highly efficient and many of the breakthroughs involved catalytic developments. The future success of biorefinery will require a design of a new generation of catalysts for the selective processing of carbohydrates and lignin. Ecology dangerous and corrosive-active catalysts on the bases of inorganic acids and alkali solutions should be changed on the more technologically suitable solid catalysts. The design of efficient multifunctional catalysts opens the new possibilities in biomass processing since they allow to carry out the multisteps transformations to the target products by one-stage conversion. The integration of different catalytic processes in one technological cycle allows to perform a wasteless processing of all components of lignocellulosic biomass to biofuels and platform chemicals . "Международное сотрудничество в сфере биоэнергетики", Москва, 2013

46. 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

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