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ISSN 2070 0504, Catalysis in Industry, 2011, Vol. 3, No. 1, pp. 13. Pleiades Publishing, Ltd., 2011.

. Original Russian Text S.D. Varfolomeev, 2011, published in Kataliz v Promyshlennosti.

BIOCATALYSIS

Biofuels: Energy Carriers from Renewable Raw Material


S. D. Varfolomeev
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, ul. Kosygina 4, Moscow, 119334 Russia Faculty of Chemistry, Moscow State University, Leninskie gory 1, str. 3, Moscow, 119991 Russia
Received July 8, 2010

DOI: 10.1134/S2070050411010168

Renewable energy, the stores of which are replen ished naturally by the flow of solar radiation arriving at the Earths surface, has satisfied mans main needs (heat, food, fuel) throughout the development of human civilization. In a very short period of human development (19th20th centuries) a notable contri bution was made to this natural process by the addi tional sources of solar energy preserved for millions of years as coal, oil, and gas. In recent decades, nuclear energy, the development of which began in the second half of the 20th century, joined these. The world history of hydrocarbon use on a global historical scale is as short as it is dramatic: the limits of traditional fuel hydrocarbon fuel energy had become apparent by the second half of the 20th century, and the world had begun to devote considerable attention to renewable sources of energy, due mainly to the depletion of fossil resources and the substantial eco logical damage from traditional sources of energy. One of the first to point this out was Nobel Prize winner Academician N. N. Semenov (1974) [1]. The relatively low densities of energy flows present technological difficulties for the application of renew able energy. The production of electricity at modern hydropower plants nevertheless employs quite tradi tional methods. The technological procedure that provides mankind with foodagricultureis almost completely based on the Suns energy. Even today, agriculture remains a branch of the power industry (in the broad sense of the term) to which there is no alter native, as it involves the technological synthesis of energy rich compounds that provide fuel for both ani mals and man. The above methods for utilizing solar energy have become widespread because convenient and practica ble methods for their application were developed and corresponding modern hydroelectric and agricultural technologies were created. New, technologically sig nificant ways of applying solar energy have been devel oped in recent decades: the direct transformation of light into electrical energy (through the use of trans formers and solar panels), the conversion of wind energy, the production of electrical energy in concen trated flows of light through heat engines, and the pro
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duction of biofuel. These methods for the use of renewable energy have now been commercialized on a grand scale and have become genuine rivals of tradi tional fuels [2, 3]. The amount of renewable energy electrical gener ating capacity introduced in Europe in 2009 (wind, solar panels, hydropower plants, biofuel, concentrated sunlight) is 1.35 times greater than the new capacity based on traditional energy carriers (gas, oil, coal, nuclear energy). Our times are a turning point at which the overall introduction of new capacity based on the use of renewable energy has exceeded the over all introduction of capacity associated with traditional energy sources based on fossil fuel. Most of the worlds oil goes to produce liquid fuel for automobiles. Demand for this type of energy carrier is constantly growing in as a result of the automobilization of China, India, and South America. Technologies for the production of automobile fuel from bioresources continue to develop exponentially. Sources of raw mate rial are becoming ever more diverse: raw grain, farm wastes, lignocellulosic materials, microscopic algae, and so on. Biofuels are energy rich compounds used as fuels but obtained from renewable raw materials by chemical and biotechnological methods [4, 5]. This wide range of compounds includes hydrogen, methane, ethanol, biodiesel fuel, butanol, bioketals, bio oil (products of bio mass pyrolysis), bionitrile, and so on. Total world pro duction of biofuels for automobiles is doubling every 2.5 3.5 years. The figure shows data on the dynamics of world oil production (curve A), biodiesel fuel, and bioethanol (curve B). The total production of bioethanol and biodie sel fuel in the coming 1525 years could compare to the volumes of the total world oil production. It should be always remembered that the amount of fossil fuels is limited. In addition, the production of raw hydrocarbons is becoming more expensive. World demand for raw hydrocarbons is stabilizing and will soon begin to wane. This will occur not in the indefi nite future, but in the next 1015 years. In Russia, investigations on renewable energy and biofuels are nowadays concentrated mainly in the institutions of the Russian Academy of Sciences and in Moscow State University. The strategy behind these

2 Volume of production, millions of metric tons 10000

VARFOLOMEEV

A 1000

100 B 10 2000 2005 2010 2015

Oil production Production of bioethanol and biodiesel fuel 2020 2025 2030 Year

Figure. Data on the dynamics of (A) world oil production and (B) bioethanol and biodiesel fuel production. The dashed line is an extrapolation of two possible ways of increasing production.

efforts was laid out by Academician N. N. Semenov in 1978, creator of the USSR Academy of Sciences Sci entific Council for Finding New Ways of Using Solar Energy. The council comprised sections on photoelec tricity (headed by Corresponding Member and later Academician and Nobel Prize winner Zh.I. Alferov), biofuel, wind energy, and investigating the possibilities for the transformation of solar energy by heat engines. A unique industry for producing bioethanol via the transformation of lignocellulosic raw material [6] was established in the Soviet Union in those years, and industrial facilities for producing biogas from farm wastes were constructed. Having a relatively favorable climate for agriculture and the cultivation of forests, Russia has unique possi bilities for the production of bioenergy carriers. In terms of energy content, the wastes from todays agri culture alone could enable the country to increase its production of automobile fuel many times over. Every year, Russia produces around 100 million metric tons of grain and 120200 million metric tons of waste in the form of plant biomass. In terms of energy content, this source corresponds to 5595 million metric tons of gasoline. The countrys total annual volume of agri cultural waste and waste from the timber industry is 300350 million tons. For the sake of comparison, 3033 million metric tons of gasoline is consumed in Russia annually. Renewable energy is the key to the development of Siberia and the Russian Far East. China is following the very same route by orienting its northwestern regions toward using renewable sources of energy. Growth in the production of renewable energy is determined primarily by its economic demand. In

terms of cost, biofuels are now comparable to tradi tional automobile fuels. The price of one liter of fuel ethanol in the United States and Europe is $0.50.7, while that of one liter of biodiesel fuel is $0.50.8. It has been shown that once the price of oil rises above $60 a barrel, biofuel production becomes economi cally profitable. Renewable energy and bioenergy carriers have sev eral undeniable advantages: virtually infinite volume of resources and acces sibility in any region of the world; environmental friendliness, the fundamental solution to problems associated with the planets glo bal warming and the release of greenhouse gases; independence from oil and gas producing countries; a more even distribution of energy production and consumption and elimination of the need to use systems with extremely high energy densities; elimination of resource intensive and vulnerable systems of transporting energy (transmission lines, pipelines, and so on). These advantages make renewable energy the only one we need and to which there is no alternative. The conversion to new full scale sources of energy is now underway. Technologies for the production of bioenergy carri ers are being developed around the world. There are three basic problems in producing a new generation of fuels: 1. The processes of biomass pretreatment. Plant biomass is a blend of complicated chemical composi tion in which biopolymers of the cellulose, hemicellu lose, and lignin types predominate. A qualitatively new level of the processes of depolymerization and struc tural unification of renewable raw material is required. 2. As in most chemical processes, catalysis is the key problem in moving the process to a realistic tech nological level. The wide variety of chemical struc tures and the complex composition of renewable raw material makes the problem of creating catalysts extremely complicated. Realistic solutions in this field are to use microbial and biotechnological processes or a combination of chemical and biotechnological stages. 3. Modern techniques include highly efficient stages for the separation of reaction products. The most vital of these are membrane processes for com pound separation. This special issue of the journal is dedicated to con sidering the above problems of biofuel production. The production of fuel from biomass is based on contemporary achievements in catalysis, microbiol ogy and biotechnology, chemical enzymology, and the physics and chemistry of modern separating processes. The interdisciplinary character of the problem is reflected by the articles presented in this special issue.
CATALYSIS IN INDUSTRY Vol. 3 No. 1 2011

BIOFUELS: ENERGY CARRIERS FROM RENEWABLE RAW MATERIAL

The depolymerization of natural biopolymers (cel lulose, hemicellulose, lignin, and proteins) is the most limiting and energy and labor consuming stage of converting biomass to fuel. Now under development are various mechanical and chemical processes, fer mentation methods of hydrolysis, and techniques for ultrasound pretreatment. The production of bioalcohols and biodiesel fuel is one line of todays scientific research and engineering. The processes for producing ethanol, butanol, and esters of fatty acids are subject to continual improve ment. In this issue of the journal, we discuss the cre ation of new heterogenous biocatalysts and sources of lipids, and methods for transforming them into biodiesel fuel. The variety of biofuels is continually growing. By products from the production of bioalcohols and biodiesel fuel, e.g., glycerol and pentosans, can be chemically modified into bioketalshigh octane additives to traditional fuels for internal combustion engines. Hydrogen power is one todays most promising fields. Hydrogen is the fuel richest in energy and most environmentally friendly. The problem lies in hydro gen being a poorly accessible and expensive fuel. Con temporary methods of hydrogen production are based on the use of natural gas. The microbiological synthe sis of hydrogen from biomass or the creation of an energy cycle of the biophotolysis of water with the sep

arate production of hydrogen and oxygen is attractive highly intriguing scientific and technical problem. The energy of the obtained hydrogen can be directly con verted into electrical energy using state of the art enzymatic fuel elements. Any scientific or technical problem in the field of large scale fuel technology is associated with com pound separation. The present day solution to such problems is based on the processes of membrane sep aration, to which one of the articles of this special issue is dedicated. REFERENCES
1. Semenov, N.N., Izbrannye trudy (Selected Transac tions), Moscow: Nauka, 2006, vol. 4. 2. Moiseev, I.I., Plate, N.A., and Varfolomeev, S.D., Herald Russ. Akad. Sci., 2006, vol. 76, no. 5, pp. 427437. 3. Varfolomeev, S.D., Moiseev, I.I., and Myasoedov, B.F., Vestn. Ross. Akad. Nauk, 2009, vol. 79, no. 7, pp. 595 607 (Herald of the Russian Acad. Sci. (Engl. Transl.), 2009, vol. 79, no. 4, pp. 334344). 4. Varfolomeev, S.D., Kalyuzhnyi, S.V., and Medman, D.Ya., Usp. Khim., 1988, vol. 57, no. 7, pp. 12011231. 5. Varfolomeev, S.D., Efremenko, E.N., and Krylova, L.P., Usp. Khim., 2010, vol. 79, no. 6. 6. Kholkin, Yu.I., Tekhnologiya gidroliznykh proizvodstv (Technology of Hydrolysis Productions), Moscow: Lesnaya promyshlennost, 1989.

CATALYSIS IN INDUSTRY

Vol. 3

No. 1

2011