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2015/1
Study of impact of various cellulosic feedstock pretreatment techniques on degree of cellulose crystallinity
Chemical sciences

Authors: Artem A. LITVIN graduated from Astrakhan State Technical University in 2013 as a BSc with a specialty of “Chemical engineering and biotechnology”. Currently he is working on Master thesis at Gubkin Russian State University of Oil and Gas. He is also an engineer of the department of Physical and Colloidal Chemistry. The area of scientific interests includes synthesis of ionic liquids and application of ionic liquids for desulphurization of hydrocarbon fuels, pretreatment of lignocellulosic biomass for further obtaining of high-energy products. He is an author of 10 scientific publications. E-mail: artemich92@mail.ru
Iakov A. MASIUTIN graduated from Gubkin Russian State University of Oil and Gas in 2012 as a MSc in Chemical Technology and Biotechnology. Currently he is a PhD student at Gubkin Russian State University of Oil and Gas, engineer of the department of Physical and Colloid Chemistry of Gubkin Russian State University of Oil and Gas. He is a specialist in the field of technologies of biofuels production, synthesis of ionic liquids, application of spectroscopic methods for analysis of petroleum and petroleum products. He is an author of more than 30 scientific publications. E-mail: YMA1989@mail.ru
Andrei A. NOVIKOV graduated from Perm State University in 2007 as a MSc in chemistry. He completed his postgraduate studies at Gubkin Russian State University of Oil and Gas in 2010. He is a PhD in chemistry, head of the Center for Nanodiagnostics at Gubkin Russian State University. Andrei Novikov is a specialist in the fields of organic chemistry, microbiology, and nanodiagnostics. He is an author of more than 40 scientific publications. E-mail: gubkin.biotech@gmail.com
Vladimir A. VINOKUROV graduated from Moscow Institute of Petrochemical and Gas industry in the specialty of “Technical engineer”, in 1975 he completed his postgraduate studies ibidem. He is a doctor of Chemical Sciences, Professor, head of the department of Physical and Colloid Chemistry at Gubkin Russian State University of Oil and Gas. Vladimir Vinokurov is a prominent specialist in the field of surface chemistry and disperse systems chemistry, synthesis and stabilization of nanoparticles and biotechnology. He is an author of over 200 scientific publications. E-mail: vinok_ac@mail.ru

Abstract: The impact of various pretreatment techniques of cellulosic feedstock (microcrystalline cellulose Avicel, pine sawdust) on the degree of cellulose crystallinity was studied. By means of powder diffractionit was established that the highest impact on lowering of the cellulose crystallinity degree was achieved through pretreatment by the mixture of ionic liquidsand by preliminary γ-irradiation with the dose of absorbance of 100 kGy. The substrates obtained through pretreatment could further be subjected to hydrolysis to glucose, which in turn is a source of ethanol, butanol-1, 2,5-dimethylfuran, and some other compounds that could be used as high-energy additives to conventional hydrocarbon fuels

Index UDK: 663.534 + 577.3 + 544.478.42 + 661.728.7

Keywords: cellulose, crystallinity, irradiation pretreatment, ionic liquids, oxidative pretreatment, hydrolysis, powder diffraction

Bibliography:
1. Lynd L.R., Weimer P.J., van Zyl W.H., Pretorius I.S. Microbial cellulose utilization: Fundamentals and biotechnology. Microbiol. Mol. Biol. Rev., 2002, vol. 66, issue 3, p. 506–577.
2. Mansfield S.D., Mooney C., Saddler J.N. Substrates and enzyme characteristics that limit cellulose hydrolysis. Biotechnol Prog., 1999, vol.15, issue 5, p. 804–816.
3. Andersson S., Serimaa R., Paakkari T., Saranpää P., Pesonen E. Crystallinity of wood and the size of cellulose crystallites in Norway spruce (Picea abies). The Japan Wood Research Society, 2003, p. 807–811.
4. Zhao H., Kwak J.H., Wang Y., Franz J.A., White J.M., Holladay J.E. Effects of Crystallinity on Dilute Acid Hydrolysis of Cellulose by Cellulose Ball-Milling Study. Energy & Fuels, 2006, vol. 20, p. 807–811.
5. Aleshina L.A., Glazkova S.V., Lugovskaya L.A., Podoynikova M.V., Fofanov A.D., Sili- na E.V. Contemporary notions on structures of celluloses. Khimiya rastitelnogo syrya [Chemistry of plant feedstock], 2001, no. 1, p. 5–36 (in Russian).
6. Xiang Q., Lee Y.Y., Pettersson P.O., Torget R.W. Heterogeneous aspects of acid hydrolysis of α-cellulose. Biotechnology for Fuels and Chemicals. — Humana press, 2003, pp. 505–514.
7. Heinze T., Schwikal K., Barthel S. Ionic liquids as reaction medium in cellulose functionalization. Macromol. Biosci., 2005, vol. 5, p. 520–525.
8. Yang C. et al. Effect and aftereffect of γ radiation pretreatment on enzymatic hydrolysis of wheat straw. Bioresource technology, 2008, vol. 99, issue 14, p. 6240–6245.
9. Masiutin Ia.A., Golyshkin A.V., Litvin A.A., Novikov A.A., Vinokurov V.A. Pretreatment of cellulosic substrates by acetate- and chloride-based ionic liquids and their mixtures. APCBEE Procedia (2014 5th International Conference on Biology, Environment and Chemistry (ICBEC 2014), 29— 30 October 2014, San Diego, USA), vol. 11, p. 48–53. ISSN: 2212–6708.
10. Lesin V.I., Pisarenko L.M., Kasaikina O.T. Colloid catalysts based on iron (III) oxide. 1. Hydrogen peroxide decomposition. Kolloidnyy zhurnal [Colloid journal], 2012, vol. 74, no. 1, p. 90–95 (in Russian).
11. Kasaikina O.T., Pisarenko L.M., Lesin V.I. Colloid catalysts based on iron (III) oxide. 2. Features of catalytic oxidation of palm oil. Kolloidnyy zhurnal [Colloid journal], 2012, vol. 74, no. 4, p. 503–508 (in Russian).
12. Berberov A.B., Masyutin YА.A., Afonin D.S., Borzaev H.H. Application of the colloid catalyst based on iron (III) oxide and polymetallic nanocatalyst (Fe-Co-Ni) for modification of lignocellulose structure. Izvestiya Kabardino-Balkarskogo nauchnogo centra RAN [Proceedings of Kabardino-Balkar Scientific Center of RAS], 2013, vol. 1, no. 6 (56), p. 72–78 (in Russian).

2014/2
Study of oxidizability of cellulosic raw material with hydrogen peroxide over colloidal cata-lyst based on iron oxide (iii)
Oil and gas processing, chemistry of oil and gas

Authors: Yakov A. MASYUTIN completed Master’s degree Gubkin Russian State University of Oil and Gas in 2012, specializing in „Chemical Technology and Biotechnology”. He is currently doing a postgraduate course of studies at Gubkin Russian State University of Oil and Gas and occupies the position of engineer of the Department of Physical and Colloid Chemistry of the named university. He is a specialist in the sector of biofuels synthesis of ionic liquids, application of spectroscopic methods for the analysis of petroleum and petroleum products. He is author of 20 scientific publications.E-mail: YMA1989@mail.ru
Roman I. KLYUKIN completed Bachelor’s degree in Kazakhstan branch of the Lomonosov Moscow State University University (Astana) in 2012, majoring in „Ecology and NatureManagement”. He is currently doing a graduate course at Gubkin Russian State University of Oil and Gas and occupies the position of engineer of the Department of Physical and Colloid Chemistry of the named university. The area of his research includes environmental impact assessment of oil and gas industry, including pipeline transportation, as well as methods of producing alternative energy sources.E-mail: klyukin_roman@bk.ru
Andreу A. NOVIKOV completed Master’s degree of the Perm State University majoring in „Chemistrу” in 2007. In 2010, he graduated from the graduate school at Gubkin Russian State University of Oil and Gas. He is Candidate of Chemical Sciences, Head of the Laboratory „Center for Nanodiagnostics” Gubkin Russian State University of Oil and Gas. He is a specialist in the field of organic chemistry, microbiology and nanodiagnostics, author of more than 30 scientific publications. E-mail: gubkin.biotech@gmail.com
Vladimir A. VINOKUROV graduated from Gubkin Moscow Institute of Petrochemical and Gas Industry in 1972 as „Manufacturing Engineer”. He is Doctor of Chemical Sciences, Head of the Department of Physical and Colloid Chemistry at Gubkin Russian State University of Oil and Gas. He is well-known a specialist in the field of surface chemistry and disperse systems, synthesis and stabilization of nanoparticles, and biotechnology. He is author of over 200 scientific publications.:E-mail: vinok_ac@mail.ru

Abstract: We have studied the oxidation of pre-radiated and original cellulosic feedstock (pine sawdust, bamboo chips) with dilute solutions of hydrogen peroxide over a catalyst based on colloidal iron oxide (III). As a result, it was found that the combined pretreatment by radiation and catalytic oxidation with hydrogen peroxide is an effective method of preparation of lignocellulosic feedstock for hydrolysis. This is due to the reduced content of lignin, the degree of polymerization and the crystallinity of cellulose. The byproducts (water solutions of oxidative degradation products of lignin) obtained during pretreatment can be used as plant growth stimulants or additives for animal feed. Analysis of the by-products by the me- thod of capillary electrophoresis revealed single, two-and tribasic carboxylic acids, while the gas chromatography-mass spectrometry analysis confirmed the presence of aldehydes, alcohols, esters, and nitrogen-containing heteroatomic compounds besides carboxylic acids

Index UDK: УДК 663.031.7 + 544.478.42 + 66.094.3.097 + 66.097.3-039.672

Keywords: lignocellulose, irradiation pretreatment, hydrogen peroxide, colloid particles of iron (III) oxide, carboxylic acids

Bibliography:
1. Sun R.C. Cereal Straw as a Resource for Sustainable Biomaterials and Biofuels. Chemistry, Extractives, Lignins, Hemicelluloses and Cellulose. Publ.: Elsevier, 2010, 300 р.
2. Tretyakov V.F., Makarfi Yu.I., Tretyakov K.V. Catalytic conversion of bioethanol into hydrocarbon fuels. Kataliz v promyshlennosti [Catalysis in industry], 2010, no. 5, pp. 11–32. (in Russian).
3. Varfolomeev S.D., Moiseev I.I., Myasoedov B.F. Energy carriers obtained from renewable raw materials. Vestnik Rossiyskoy akademii nauk [Bulletin of Russian Academy of Sciences], 2009, vol. 79, no. 7, pp. 595–607. (in Russian).
4. Makarfi Yu.I., Trushin A.A., Tretyakov V.F. Resource-saving and energy-saving technologies in chemical and petrochemical industry: Tezisy dokladov pervoy mezhdunarodnoy konerencii RKhO imeni D.I. Mendeleeva. [Abstracts of the 1st international conference of Russian Chemical Society named after Dmitriy Mendeleev, Moscow], 2009, p. 48. (in Russian).
5. Berberov A.B., Masyutin Ya.A., Afonin D.S., Borzaev H.H. Application of the colloid catalyst based on iron (III) oxide and polymetallic nanocatalyst (Fe-Co-Ni) for modification of lignocellulose structure. Izvestiya Kabardino-Balkarskogo nauchnogo centra RAN [Proceedings of Kabardino-Balkar Scientific Center of RAS], 2013, vol. 1, no. 6 (56), pp. 72-78. (in Russian).
6. Lesin V.I., Pisarenko L.M., Kasaikina O.T. Colloid catalysts based on iron (III) oxide. 1. Hydrogen peroxide decomposition. Kolloidnyy zhurnal [Colloid journal], 2012, vol. 74, no. 1, pp. 90-95. (in Russian).
7. Kasatkina O.T., Pisarenko L.M., Lesin V.I. Colloid catalysts based on iron (III) oxide. 2. Features of catalytic oxidation of palm oil. Kolloidnyy zhurnal [Colloid journal], 2012, vol. 74, no. 4, pp. 503-508. (in Russian).
8. Kropotkina V.V., Khmelyova A.N., Vereshchagin A.L. Pod red. Leonov G.V. The mechanism of growth-promoting action of ultra-low doses of natural organic acids. Innovatsionnye tekhnologii: proizvodstvo, economika, obrazovanie: materialy Vserossiyskoy nauchno-prakticheskoy konferencii 24 Sentyabrya 2009 goda [Innovative Technologies: production, economics, education: materials of All-Rusaian scientific and practical conference. September, 24, 2009]. Altai State Technical University, BTI. — Biysk: Publishing house of Altai State Technical University, 2009, pp. 372–375. (in Russian).
9. New corrective feed additive „Ekolin-4” for high-producing cows. G.V. Naumova, A.I. Ko-zinets, N.L. Makarova, T.F. Ovchinnikova, N.A. Zhmakova, O.G. Golushko. Prirodopolzovanie [Natural management], 2011, Issue 20, pp. 117-122. (in Russian).