Science of Central Asia

ISSN 2079-5467

Science of Central Asia

www.scientificfund.kz

july - august 2010

SCIENCE SCIENCE

Private Fund for Supporting of Science and Technologies Частный фонд поддержки науки и технологий

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To the 90 – year anniversary of the Academician of the National Academy of Sciences of the Republic of Kazakhstan, professor S.Z. Zimanov

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alyk Zimanovich Zimanov is the greatest scientist, Academician of the National Academy of Sciences of the Republic of Kazakhstan. The course of life and scientific activity of the veteran of war, outstanding scientist S.Z. Zimanov are sated by bright historical events. Salyk Zimanovich Zimanov was born on February, 19, 1921 in Gurjev (nowadays - Atyrau). He has gone on front at 20-year-old age and participated in speeding up of the rivers Bug, Dnepr and Oder. He took part in fights for liberation from fascists of various cities and villages of USSR and the countries of Europe, he had wounds. In the end of war the fighting officer ordered the artillery of the mechanized brigade. In victorious May 1945 he became the participant of a meeting of allied armies on Elba. After demobilization Zimanov has decided to become the lawyer. He has passed a way from the trainee in regional Office of Public Prosecutor to the inspector on especially important issues of Office of Public Prosecutor of the Kazakh Soviet Socialist Republic in Alma-Ata. Then he defends the candidate and doctor's dissertations. In 50-60th years he took part in the large researches devoted to political and legal history to the pre-Soviet Kazakhstan. In 70th years in the centre of scientific interests of academician Zimanov there were problems of statehood of the Kazakh people and other people of Central Asia. The uncommon talent of the scientist, analyst and the orator has revealed in days of his parliamentary activity. In 1990 S. Zimanov has been elected by the deputy of the Supreme body of Republic and soon put forward in number of active legislators. He has been elected by the chairman of one of Parliament committees, headed the commission on preparation of the project of the Declaration on the state sovereignty of the Kazakh Soviet Socialist Republic. His scientific interests cover the theory and history of political and legal system, federative state, constitutional law, state law and political science. He is the author more than 200 scientific works, from them 12 monographies, the head and the author of preparation and the edition of the three-volume book «History of the state and the right of the Soviet Kazakhstan». His researches concerning

political history, federal device of the USSR and politicallegal thought of the people of Kazakhstan and others republics of the Central Asia represent the invaluable contribution to a science. In his works the complex and integral historic and political reality which has developed before and after revolution on 1917 in Russia is reproduced. In history of independent Kazakhstan Zimanov is in number of those who prepared the historical Constitutional law “About the state independence of the Republic of Kazakhstan”. He supervised over expert group under the project of the Constitution of Kazakhstan of 1993. Also he headed two committees in the Supreme body. The parliament operational experience in the first years of sovereign Kazakhstan has been generalized by him in book “The Constitution and Parliament of the Republic of Kazakhstan” (1996). From 1995 to 2005 Zimanov was the rector of the created by him together with colleagues of the not state Academic legal institute "Parasat", then - the Kazakh academic university. From 2004 he is the president of Open Company "Intellectual-Parasat" and as the scientific leader - he is the initiator of various conferences, discussions, researches. Salyk Zimanovich by right is the patriarch of a legal science and the higher juridical education of Kazakhstan. The range of his research works is wide, and the manner and style of scientific thinking are original. He is the generator of new ideas. Proceedings of Academician of National Academy of Sciences of the Republic of Kazakhstan of Zimanov S. Z have brought the considerable contribution to development of jurisprudence of Kazakhstan, its historical and modern aspects were highly appreciated by the legal public of Kazakhstan, are claimed by researchers, domestic and foreign scientists, students. He is the winner of the Presidential award of the world and the spiritual consent, the Ñh. Valikhanov's award of Academy of sciences of the Kazakh Soviet Socialist Republic, the award of Republic Kazakhstan in the field of a science. Marking anniversary year, Zimanov constantly is in work: acts with lectures, reports at conferences, prepares new proceedings.


INTERNATIONAL CHAIRMAN OF EDITORIAL BOARD Domenico Sanfilippo Professor, Chief Scientist, ENI, Refining & Marketing Division, Manager for Industrialization of New Technologies and Project Director, Italy

LOCAL CHAIRMAN OF EDITORIAL BOARD Alija S. Beisenova Professor, Academician of National Academy of Sciences of Republic of Kazakhstan, Academician of National Academy “Ecology”

INTERNATIONAL EDITORIAL BOARD Dmitry Yu. Murzin Professor, Laboratory of Industrial Chemistry and Reaction Engineering, Abo Akademi University, Turku/Åbo, Finland Vladimir V. Galvita Dr., Senior Research Scientist, Research Group Leader, Ghent University, Department of Chemical Engineering and Technical Сhemistry, Belgium Ilya Digel Dr. Aachen University of Applied Sciences, Head of Laboratory of Cell-and Microbiology. Germany Nurtay Urdabayev Dr., Ph.D. Thermo Fisher Scientific, Fremont, CA, USA Galina Xanthopoulou PhD, DSc, Professor, Institute of Materials Science, NCSR «Demokritos», Athens, GREECE Sobhy Ahmad El-Sohaimy Ph.D. Food Science and Technology Department, Mubarak City for Scientific Research and Technology Applications (MUCSAT), Egypt. Cultural and Educational Attaché-Director of the Egyptian Cultural Center, Embassy of the Arab Republic of Egypt in Kazakhstan

LOCAL EDITORIAL BOARD Salyk Z. Zimanov Professor, Academician of National Academy of Sciences of Republic of Kazakhstan Zh. Sh. Zhantaev Doctor of Physical and Mathematic Sciences, President of JSC «National Center for Space Research and Technology» Essen. A. Bekturov Professor, Academician of National Academy of Sciences of Republic of Kazakhstan Karl Baipakov Professor, Academician of National Academy of Sciences of Republic of Kazakhstan Serik S. Kirabaev Professor, Academician of National Academy of Sciences of Republic of Kazakhstan Kair A. Zhubanov Professor, Academician of National Academy of Sciences of Republic of Kazakhstan Оrazak I. Ismagulov Professor, Academician of National Academy of Sciences of Republic of Kazakhstan, Corresponding Member of Bologna Academy of Sciences (Italy)

Мukhtar M. Bakenov Professor, Academician of National Academy of Sciences of Republic of Kazakhstan Bulat E. Kumekov Professor, Academician of National Academy of Sciences of Republic of Kazakhstan Serik. K. Kozhakhmetov Professor, Doctor of Physical and Mathematic Sciences, Institute of High Technologies, Almaty, Kazakhstan Kuanyshbek B. Musabekov Professor, Doctor of Chemical Sciences, al-Farabi Kazakh National University Altay S. Amanjolov Professor, Doctor of Philology, Türkologist al-Farabi Kazakh National University Zhaken K. Taimagambetov Professor, Doctor of Historical Sciences al-Farabi Kazakh National University Mikhail K. Naurysbayev Professor, Doctor of Technical Sciences, al-Farabi Kazakh National University, Director of the Accredited Centre of Physical and Chemical Methods of Research and Analysis Tlek A. Ketegenov Professor, Doctor of Chemical Sciences, Institute of High Technologies, Almaty, Kazakhstan Zhaksantay K. Kairbekov Professor, Doctor of Chemical Sciences, al-Farabi Kazakh National University Kanat K. Shakenov Professor, Doctor of Physical and Mathematic Sciences, al-Farabi Kazakh National University Azhar A. Zhubanova Professor, Doctor of Biological Sciences, al-Farabi Kazakh National University Sagdat M. Tazhibayeva Professor, Doctor of Chemical Sciences, al-Farabi Kazakh National University Galym. K. Mamytbekov Professor, Doctor of Chemical Sciences, Institute of High Technologies, Almaty, Kazakhstan Adambek M. Tatenov Candidate of Physical and Mathematic Sciences, Director of the Kazahstan-Korean Educational Centre or InformationTelecommunication Technologies, Almaty, Kazakhstan Valentina S. Emel’anova Candidate of Chemical Sciences, Scientific Research of Institute of New Chemical Technologies and Materials, Almaty, Kazakhstan Kairat Rsymbetov Candidate of Physical and Mathematic Sciences, Central Computation Centre Director (Kazakh Railways Company) Khairolla M. Gabzhalilov President of the Research Center «Alash», Candidate of Historical Sciences, Almaty, Kazakhstan

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Журнал «Science of Central Asia» № 4 июль - август 2010 года

content

Периодичность: шесть номеров в год, www. scientificfund.kz Главный редактор Сундетбай Тунгатаров Дизайн и верстка Татьяна Рожковская Техническая подготовка Альберт Аджимуратов Адрес редакции: 050005, Алматы, ул. Тлендиева, 65, 18 Тел. +7 727 241 24 76 [email protected]

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Свидетельство о постановке на учет № 10443-Ж выдано Министерством культуры и информации Республики Казахстан 23.10.2009 г. Мнение авторов не всегда совпадает с мнением редакции. Ответственность за содержание рекламных материалов несет рекламодатель. Перепечатка материалов, а также использование в электронных СМИ возможны только при условии письменного согласования с редакцией. Отпечатано в типографии DPI, Республика Казахстан, г. Алматы, ул. Кожамкулова , 200 +7 (727) 2 937 444, 2 937 037, 2 935 770 Тираж 500 экземпляров почтовый индекс 74358 Учредитель и издатель Частный фонд поддержки науки и технологий «Sciencе»

CATALYTIC TECHNOLOGIES, FROM THE DAWN OF THE IDEA TO THE INDUSTRIAL IMPLEMENTATION D. Sanfilippo. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 THE KAZAKH BIY COURTS WERE KEPT AND REMAINED IN THE MEMORY OF GENERATIONS AS INDEPENDENT, PROFESSIONAL AND WISE JUSTICE S.Z. Zimanov. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 CONVERSION OF REAL ASSOCIATED GASES BY CARBON DIOXIDE OVER THE KMR-8 СATALYST Sh.S. Itkulova.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 СOMPLEX FORMATION OF METALPHAEOPHYTINS WITH POLY-4-VINYLPYRIDINE HYDROGEL E.A. Bekturov, Zh.K Korganbayeva., T.K. Jumadilov. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 Дмитрий Мурзин интервью. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 Галина Ксандопуло интервью. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 Galina Xanthopoulou interview.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

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INSTRUCTIONS TO AUTHORS

SELF-PROPAGATING HIGH-TEMPERATURE SYNTHESIS AS METHOD OF CATALYSTS PRODUCTION G. Xanthopoulou. . . . . . . . . . . . . . . . . . . . . . . . . . 45 КАТАЛИТИКАЛЫҚ ӨҢДЕУ АРҚЫЛЫ ТАБИҒИ ГАЗДАН СИНТЕЗ-ГАЗ АЛУ

Т.С. Байжуманова.. . . . . . . . . . . . . . . . . . . . . . . . . 56 MACROMOLECULAR COMPLEXES OF HYDROGELS E. Bekturov, R. Iskakov.. . . . . . . . . . . . . . . . . . . . 60 INFLUENCE OF PLASTIFIERS CONCENTRATION ON THE RELATIVE CHANGING OF SURFACE TENSION ON THE BONDERY SOLID – LIQUID K.G.Mukhamedov, S.S. Khamraev . . . . . . . . . . . 65 OXIDATIVE CONVERSION OF C3-C4 ALKANES TO ACETONE S.A. Tungatarova. . . . . . . . . . . . . . . . . . . . . . . . . . 69 MAKHMUD KASHGARY (1029/39-1101) THE OUTSTANDING CENTRAL ASIAN PHILOLOGIST OF THE XI CENTURY A.S. Beisenova. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

Papers and short communications will be published within two or three months after receipt. Please, send your papers as attached Word file(s) to [email protected]. The paper should include the most relevant and new results together with the main conclusions of the research work. The length of the paper is not limited. Papers should be written in English (preferably) (or Russian and Kazakh) and use SI units. Manuscripts should be typed in singlecolumn format of A4 (297 x 210mm) paper. The document has margins: (2 cm) Top, (2 cm) Bottom, (3 cm) Left, (1,5 cm) Right. All text should be in Time New Roman 12pt, 1,5-spaced and justified. The paper should be arranged in the following format: full title; list of the authors and affiliation with address for correspondence (post and e-mail); abstract; keywords; introduction; sections, suitably subdivided under headings; conclusions; acknowledgements (if necessary); references. Write the title in bold characters and capitalize the words. No abbreviations should be used in the title. A single line space should separate paragraphs and the same should separate text from tables or figures. The table should fit within the text column width and should use 10-12pt Times New Roman. All tables and figures must be included with the text in a single Word Document. Tables (if any) should be numbered consecutively and each should have a caption. References should be numbered in the order of appearance (brackets [1]). Please use the following format for references: 1. K. Jung, S. Park, Appl. Catal. B 25 (2000) 249. 2. J.R. Rostrup-Nielsen, Catalytic Steam Reforming, Springer, Berlin, 1984. 3. F. E. Herkes, U.S. Patent 4885391 (1989).

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Extracted from Fauser Award Lecture – Palermo, September 18, 2010

CATALYTIC TECHNOLOGIES, FROM THE DAWN OF THE IDEA TO THE INDUSTRIAL IMPLEMENTATION D. Sanfilippo After forty years of R&D in Snamprogetti/Eni. [email protected]

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Contents Drivers of Catalysis for development 1. Through catalysis to the society needs 1.1. Role of Catalysis in Oil Refining 1.2. Role of Catalysis in Petrochemistry and Chemi cals production 1.3. Role of Catalysis in Environment Preservation 2. Catalytic processes development: the long journey of an idea 3.1. The explorative and definition phase 3.2. The intensive and development phase 3.3. Projects survival and success rate 3.4. Multidisciplinarity mandates integration Conclusions Summary Catalysis has reached a noteworthy degree of maturity in the industrial applications and continues to produce innovation that is reflected in a significant contribution to the development of the modern society. This goal is achieved thanks to the closest synergy of the scientific understanding of catalytic phenomena and the scale-up of the gained knowledge into commercial applications. The role of catalysis in oil refining, in petrochemicals production, and in environmental protection is outlined. The scale up of an idea through the discovery, definition, and development phases is described. For exemplifying typical scale up routes, a series of case histories is presented, narrating a chain of connected technologies development, illustrating their №4 july - august

commercial and scientific motivations and the methodologies followed. The birth and growth of some technologies like MTBE synthesis and other etherifications, paraffins and ethylbenzene dehydrogenation is shown.

Drivers of Catalysis for development Since ancient times, catalytic processes were applied in order to improve humankind lifestyle. Fermentation (and therefore bio-catalysis) allowed Noah to produce his wine [1] or the Sumerian husbandmen to brew their beer [2]. Primordial catalysts were used for preparing pigments, inks, soaps that have allowed the civilization progress and the human culture growth. The social benefits of chemical transformations are related indeed to their technological implementation. The studies finalized to develop and scale-up catalytic processes are, by definition, application oriented: as a consequence the target of industrial catalysis is to make concrete innovations in better processes resulting in better economics, better utilization of raw materials and energy as well in improving the environmental impact. Chemical Catalysis is an essential tool for chemicals and materials production, for fuel and other energy conversion systems, for combustion devices, for fuel cells, and for pollution control systems. Often it is the key to making an entirely new technology or transmitting new life into obsolete or mature technologies. Additionally to the traditional need for productivity improvements, environmental drivers, energy saving, and


industrial safety bring new aspects to the importance of catalytic innovation [3]. More than 90% of all molecules of current transportation fuels at some point during their manufacture have passed over at least one catalyst, some 80% of all chemical products are manufactured with the aid of catalysis and more than 20% of all industrial products rely on catalytic reaction technology [4, 5]. The term “catalyst” has also migrated from the world of science to everyday spoken language. It is noteworthy that this term is always used with a positive meaning. “Catalyst” from the Thesaurus of The American Heritage Dictionary is something that incites or rouses to action: stimulus, fillip, goad, incitement, instigation, motivation, prod, push, spur, stimulant, provocation, activator, energizer, excitant. Catalytic processes require the existence of a very particular industry for catalyst manufacture. This sector is a highly specialized and diversified business. About 100 companies worldwide, less than 20 are the major ones, have some degree of capability in the production of catalysts on their own technologies or as toll manufacturers. The worldwide market value for catalysts was reported to be over $16 billion in 2009. Table 1 shows the value of the global catalyst market and the relevant Average Growth Rate (AGR) in the main fields and processes of current catalyst applications [6]. Since the cost of catalyst ranges typically from 0.1% (petroleum refining) to 0.22% (petrochemicals) of the product value [7], it can be estimated that catalysts induce a market of manufactured goods exceeding $7,500 billion yearly. Table 1. Global Catalyst Market Value 2003-2009 (Mil $) 2003

2006

2009

AGR 2003-09

Refining

2,464

2,682

2,946

3,3%

Petrochemicals

2,195

2,340

2,491

2,2%

Polymers

2,568

2,999

3,425

5,6%

1,276

1,621

1,965

9,0%

3,581

5,028

5,704

9,9%

12,084 14,670 16,531

6,1%

Fine Chem.& Interm and Others Environmental Total

1 Through catalysis to the society needs “Energy is the primary force and the tool needed to build the Human Culture” [8]. In our world, populated by over 6 billion of human beings, energy and goods are necessary for their survival. The human culture, developed in thousands of years, has been a tool and will continue to provide the tools for satisfying all needs (even if with some concerns on the sustainability of the current means and development rate) from the primary ones of food supply up to the electronic gadgets of a modern society. In the long view of human history, as for ancient Rome as in the following centuries, the decrease of the more accessible energy sources, such as wood, moved to exploit other sources, even considering the change of supply as a bother or a burden. Around 1880s, coal surpassed wood’s usage. Coal was, in turn, overtaken by petroleum in the first half of the 20th century. Natural gas, too, experienced rapid development into the second half of the 20th century. The higher complexity of the use of new less accessible resources (requiring new logistics and more complicated techniques of utilization/transformation) has not limited their exploitation. Fossil resources, mainly Oil & Gas, additionally do represent the raw materials of choice for all synthetic material. Basically the fossil sources are characterized by different H/C ratios ranging from 4 for Natural Gas to less than 1 for coal. The competition of raw materials traditionally based on their cost is shifting more and more on their availability (global and local distribution) and on the environmental impact in the entire production chain (LCA, Life Cycle Analysis). In this respect, industrial catalysis is assuming a determining impact as well for the selectivity to the desired product as well for the energy preservation during the producing cycle, reducing eventually also the CO2 emissions. As an average about 90% of the fossil hydrocarbons are destined to the energy production both in stationary power generation and transportation. Some 10% of hydrocarbons constitute the feed for the production of chemicals. Looking to the value chain of hydrocarbons from source to market, particularly to the one of oil and gas derivatives (Figure 1), it is easy to appreciate the important contribution given by the industrial catalysis in the major part of the transformation technologies: it is possible to identify in the figure the main steps of the chain from extraction, to the july - august №4

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Figure 1. Value chain of Oil & Gas hydrocarbons production, transportation and chemical transformation to the products required by the different market sectors. Crude oil, after stabilization and transportation to the user sites via pipelines or ocean shipping, is refined to fuels and feeds for the petrochemistry. NG from gas fields or associated with crude oil is transported to the markets via pipelines as CNG (Compressed Natural Gas) or shipped as LNG (Liquefied Natural Gas) to be regasified in the user countries. A minor part of NG is chemically converted to fundamental commodities like fertilizers and chemicals through catalytic processes. Traditionally used as LPG, NGLs (Natural Gas Liquids), the wet fraction of NG, are kindling more and more interest for their chemical conversion to high value products and also in this case, catalytic technologies are already existing or under development. The catalyst market is usually defined by the type of market served or by the type of catalyst product. From a sales perspective, the market is usually broken down into oil refining, chemical processing, and emission control. №4 july - august

1.1. Role of Catalysis in Oil Refining The fundamental drivers determining the refinery mission are: • Ensure the energetic security, covering the demand of energetic vectors and fuels. • Reduce the environmental impact: although vehicle emissions have impressively decreased in the last 40 years (emissions of a Euro 5 car are 1-2% of the ones emitted by a 1970s same performance model), the road mobility and the fossil fuel use still are between the main causes of atmospheric pollution. Legislation becomes increasingly severe mandating better fuel quality to reduce the fuel impact at local/ regional and global levels. • Ensure operation economics creating value for shareholders despite the reduction of margins due to the higher products quality mandated by law and to the deteriorating quality of oil crudes in terms of sulfur content and API gravity. Over 80 million barrel of crude oil are consumed daily worldwide and refined in about 700 refineries.


Looking better to the box “Refinery” of Figure 1, in Figure 2 it is reported an example of a complex refinery scheme. A refinery is an integrated sequence of technologies able to separate various hydrocarbon fractions, transform them in molecules suitable for the final use, and remove unwanted impurities (heteroatoms mainly S, N, O, metals). Unit operations for separation and final blending of streams produce the pool of products going to the market. Indeed straight run products from main fractionation are not suitable for the market. Most part must be further processed for removing impurities, inducing chemical transformations and give them the requested quality. As an example gasoline from topping is not only insufficient for the market need, but it is also of very poor quality. As a consequence several catalytic technologies able to transform intermediate streams into finished high quality, high value products have been developed and are currently commercialized. The target is to utilize any “part” of crude oil using technol-

ogies environmentally friendly both during operation and during the use of the final product. Reaction technology for petroleum refining consists almost entirely of catalytic processes designed to modify the components of the fractions in three ways: • Breaking big molecules in smaller ones (cracking) • Combining small molecules in larger ones (condensations) • Rearranging “parts” of molecules for getting more appropriate “structures” (isomerization) Major sectors of the petroleum refining catalyst market are catalytic cracking, hydrotreating, hydrocracking, reforming, and alkylation. The first four of these sectors employ zeolitic or metallic-based heterogeneous catalyst systems, whereas alkylation employs either sulfuric or hydrofluoric acid two-phase liquid catalyst systems [5]. The need for a more effective operation of the tailpipe catalytic converters mandates a better or total desulfurization of fuels since sulfur depresses the noble metals activity in catalytic

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Figure 2. Example of a complex refinery scheme july - august №4


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muffler. Better knowledge of sulfur containing molecules and above all new catalysts and optimized reactor design in hydrotreating are able to bring sulfur in gasoline and diesel oil to less than 5 ppm. A very important global aspect of the technological pattern is that crude oil has a ratio H/C lower than the one of the commercial products (gasoline, jet, gasoil, LPG). As a consequence it is necessary or to “add hydrogen” or “reject carbon”. Since hydrogen is a chemical to be produced on purpose from the raw materials available in refinery, the hydrogen balance is a key factor for the refinery economics. Important social and economic drivers for new catalytic technologies in the refining sector are emerging: • The increasing severity of the legislation mandating lighter and almost sulfur-free fuels despite the deterioration of the quality in terms of sulfur content and °API of crude oils available to the refineries. • The use of the bottom-of-the-barrel, due to the declining fuel oil demand and use • The need/opportunity to bring to the market unconventional heavy crudes, like the Venezuelan Orinoco crudes and Canadian bitumen or tar sands preserving the high quality of the products. The new opportunity for biofuels from renewable resources like ethanol (blended as such or ETBE), Bi-

odiesel (methyl-esters of fatty acids), or Green Diesel (hydrocarbon derivative from vegetal oils) [9] are fostered by industrial catalysis.

1.2. Role of Catalysis in Petrochemistry and Chemicals production Starting from a relatively low number of carbon and hydrogen sources, petrochemistry covers the production of over 70,000 intermediates and end-users products in all sectors of the modern societies. Figure 3 shows the main cycles of petrochemistry involving the first generation intermediates, the second generation ones up to the final products families for the end user. Industry of “big intermediates” and of the petrochemical downstream is mainly based on olefins and aromatics derived generally from C2-C4 paraffins in NG and refinery fractions via steam cracking (noncatalytic, even if catalysis is expected to play a future role) and catalytic reforming. Chemical Industry can be seen as a value chain: products from one technology become the feed of a subsequent one. At each step the value of the products increases “creating value”. Industrial Catalysis accounts for large part of the total sales ($1,720 billion in 2002, global) of the Chemical Industry main sectors as in Table 2 [10]. Ethylene and propylene derivatives are the basis of the chemical industry commodities and C4–C5 ole-

Figure 3. Main production cycles in Petrochemistry value chain №4 july - august


fins are transformed into high quality fuel components [11]. Unfortunately olefins production requires sophisticated technologies and is extremely costly in terms of both Capex (Capital Expenditure) and Opex (Operating Expenditure). The chemical processing catalyst market includes oxidation, hydrogenation, dehydrogenation, ammoxidation, oxychlorination, organic synthesis, etherification, esterification, ammonia, hydrogen, methanol synthesis and polymerization. The use of metal and metal oxide catalysts predominates in the non-polymerization categories of this segment. Zeolites are also used in commercial petrochemical operations such as the isomerization of xylenes, the disproportionation of toluene, and the production of various para-substituted aromatic compounds [12]. Table 2. Percent distribution of chemical sales on global scale in 2002. % Commodities

%

51

Petrochemicals

42

Inorganic Chemicals

9

Specialties

49

Performance Chemicals

22

Life Science Chemicals

27

Classical polymers such as polyethylene, polypropylene, and polystyrene are of great interest for science and industry. Catalysts used in polymerization depend on the type of general reaction technology (catalytic or free radical) employed. Catalysis is the soul of the polymerization of olefins, dienes and styrene conferring onto the polymer the desired properties. Polymers are the most extensively used plastics, and they show an above-average growth rate as materials. This increase is caused largely by new catalysts which are able to tailor the polymer structure and, by this, the physical properties. Catalytic olefin polymerization has made great steps forward over last few years. New metallocene or late-transition complexes have contributed enormously to the increase in catalytic activity and to the formation of new polymers with tailored micro-

structures. Through organometallic catalysts increasing amounts of plastic materials are produced. Catalysts such as metallocenes, half-sandwich, nickel and iron complexes, are able to tailor the microstructure of the polymer chain inferring new properties to the materials [13]. One major challenge to the process industry is the utilization of remote Natural Gas and particularly methane as alternative raw material for the manufacture of big intermediates of the chemical industry and fuels. The chemical conversion of methane and of C2, C3 and C4 alkanes present as wet fraction in many NG giant fields are a first step of a potential shift from “petro-” to “gas-” chemistry [14]. A cheaper and available feed has been always a driver for innovation in the chemical industry. Attention paid to all the NG components from methane to butanes and pentanes as additional/alternative feed for chemicals and fuels comes not only from their large availability, and from their geographical distribution, that includes countries potentially in condition to develop a gas based chemistry, but also from the possibility of simplifying production processes through innovative catalytic technologies reducing costs and environmental impact. Starting from methane in NG two complementary potential routes are possible: indirect conversions in which methane is first converted into syngas in presence of water, CO2, or oxygen (followed by already existing technologies or by the development of a chain of pacing technologies from methanol or other intermediates) and the direct functionalization of methane in the presence of oxygen or Cl2, HCl or ammonia [15]. The syngas based chemistry is already well established: cheaper technology for the manufacture of syngas is a key for improving the process economics of Gas-To-Liquid plants. Syngas-based routes to petrochemicals and synfuels are characterized by high carbon efficiency, which can hardly be met by direct conversion routes [16, 17]. Apart from a few examples, very little happened in the methane conversion processes since the initial efforts of a few decades ago under the oil crises, because of a questionable economic feasibility [18], but the situation may change in the mid term. Firstly, the environmental requirements may add a premium value to the sulphur-free synfuels and secondly, the large availability of stranded natural gas in fields where transportation is a major problem. Furthermore it has become a requirement that associated gas is not being flared. The major competition to the methane chemical conversion in the exploitation of huge stranded NG reserves remains LNG (Liquefied Natural Gas) that is july - august №4

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becoming more and more convenient for the gas fields owners and investors because of the increasingly favorable economic margins helped by a steeply decreasing learning curve developed through the technology implementation in the last years. Another field of growing interest for heterogeneous catalysis is the opportunity for better production processes for more complex agrochemicals and pharmaceuticals in the fine chemical sector [19]. An important contribution to catalytic processes is given by homogeneous catalysis: it estimated that in the chemical catalytic processes, a ratio of applications of heterogeneous to homogeneous catalysis of approximately 75:25. Homogeneous catalysis processes such as hydroformylation, carbonylation, oxidation, hydrogenation, metathesis, and hydrocyanation contribute, with millions of tons, considerably to the inventory of bulk chemicals. Today, we know much about how homogeneous catalysts are assembled, how they work, and how they can be improved: thanks to research in organometallic chemistry and its techniques and methods in experimental and theoretical concerns, and thanks to progress in chemical reaction engineering in processes using homogeneous catalysts [20]. 10

1.3. Role of Catalysis in Environment Preservation Environmental catalysis refers to catalytic technologies for reducing polluting emissions. This branch of catalysis finds application not only in traditional refinery and chemical technologies, but also for the treatment of emissions in several types of manufacturing industries (power generation, electronic, agro/food, paper, leather, metal cleaning, etc.), household or indoor applications, and in emissions control from road, sea and air transportation [21]. The environmental sector has the highest AGR of the catalysts market. Its share is passing from less than 1/4 in 2003 to over 1/3 in 2009 [6]. Environmental catalysis has continuously grown in importance over the last decades not only in economic terms, but also contributing to catalysis science with new knowledge, tools, and technologies. The development of innovative “environmental” catalysts is also the crucial factor towards the objective of developing an industrial chemistry sustainable and acceptable by stakeholders. Three environment preservation strategies are available for reducing the impact of chemicals: • waste minimization, finalized to the design and development of products and processes approaching the utopian goal of “zero emissions” №4 july - august

• emission abatement, by trapping harmful effluents or converting them to harmless substances (includes automotive and industrial end uses) and • remediation, used to restore polluted sites to their natural state. Catalysts play a crucial role in controlling emissions of gaseous pollutants to the atmosphere, mainly from mobility and power generation plants. In 1989, for the first time, the market for emission control catalysts (largely for automotive emissions) exceeded the market for petroleum refining catalysts. The market for stationary emission control catalysts (especially from power plants) is also expected to grow rapidly, after a period of teething, as a result of the legislation worldwide. SCR without ammonia slip may make friendlier to the utilities industry the DeNOx technologies.

2. Catalytic processes development: the long journey of an idea Social benefits from research become real through the development of an idea from its generation up to the industrial implementation, in respect of deontological codes of conduct. Industrial research is finalized to getting innovation and creating value for the state owned or private entrusting institution. Technological innovation in an industrial context is a fundamental tool for the development and the competitive positioning of a company. Innovation arises when a new idea is generated, evaluated, demonstrated and transformed at increasing scale (scale-up) into a successful operating reality. Innovation is not a brilliant proposal, but according to the Confederation of British Industries “Innovation is the successful exploitation of new ideas”. An innovative process begins with an idea that is generated in the somebody’s mind. In the idea generation phase, individual creativity plays a fundamental role. Discovery consists in seeing what everyone else has seen and thinking what no one else has thought (Albert Szent-Gyorgi). Giorgio Vasari, historian and artist of Renaissance tells (in Le Vite) that Michelangelo in a piece of marble, available to anyone, “saw” the “figure” to be extracted from the stone and Newton certainly was not the first spectator of a dropping apple, but he could “think” through it to the universal law of gravity! The Newton case is an example of creativity in the scientific “discovery”. Additionally to the creativity there is the “inventiveness”, that implies an application of discoveries. Human progress has been always based on creativity and inventiveness that reflects the dualism Science-


Technology, two different but interconnected cultural worlds. Scale-up is the conjunction between them. Scale up allows the passage of an initial idea into innovation, through a long (and dangerous) journey. And there are only few ideas that will cover the entire way! It is believed that creativity is innate and latent in any child and the life increasingly discourages it, above all with education and job which intrinsically impose to share and see what anyone knows and sees. As a consequence between the duties of R&D managers there is the need of liberating all creative potentialities in every researcher. There are structured methodologies for improving the level of the creativity of individuals, but I don’t know any effective system (even if someone claims it!) for generating ex-novo new break-through ideas. On purpose companies and consultants, associations of industries, academic courses pay attention to the mechanisms and methodologies for stimulating (or restoring) individual creativity. Methods and practices for helping motivated persons and teams to build from known elements a new innovative route certainly do exist. In the literature, the so-called “brain storming” in well organized sessions is reported as the most effective method for improving creativity [22]. Extremely effective is the “analysis” of all available information, but the following step of “synthesis” in non traditional ways requires to switch on a lamp allowed only by the personal characteristics. There are also commercial softwares working on the “synapses principle”. Individuals’ motivation is key factor of creativity. Initial idea derives generally from the inborn tendency towards exploration together with the perception of the existence of a problem-to-be-solved. The feeling of having identified an unprecedented solution with a new product (product innovation) or with a more effectiveeconomic way of producing a known product (process innovation) produces the new idea. Certainly also in catalysis necessity of solving a problem is a powerful motivation. It is always true that “necessity is mother of invention”: the need for a more powerful gasoline pushed the race driver and mechanical engineer Eugene Houdry to develop the catalytic cracking process; strong motivations arise in the war times: the Chilean nitrates embargo to Germany boosted the Haber and Bosch studies for the fixation of atmospheric nitrogen in catalytic ammonia synthesis; catalytic reforming and alkylation allowed the RAF pilots to have available a high-octane fuel to win the battle of Britain. More generally the strategic lines (typically market driven) and the cultural background of research teams and of companies, the attention paid to the worldwide

scientific advancement, including to the “weak signals”, stimulate the fantasy towards a way of producing a completely new material, or to a simpler and less capital-intensive route of producing an existing product, or to the use of lower cost feedstocks (or waste by-products). Social concerns and evolving legislation are additional drivers pushing efforts for improved technologies. It is my opinion that the achievement of a technological success, even involving innovative catalysts, is more probable when the initial idea is already process “pulled” (e.g. the possibility of transforming “A to B”, and I do not know what catalyst could work), in respect to the catalyst “pushed” research (e.g. the availability of a “wonderful catalyst”, and I do not know for what reaction). Indeed the connections between R&D and business have evolved from a “first generation” characterized by offering of skills from R&D to a reluctant business to a second generation of specific short term requests by the business to a “third generation” of integrated vision and match of needs and skills [23]. The most recent approach enlarges the concept to the integration of resources/know how outsourced wherever available. Researchers have different attitude in respect to innovation: like for children in front of a new toy, three typical questions characterize the personal attitude of researchers: i) what’s the purpose? “to Invent”; ii) how it works? “to optimize”; iii) how it is inside? “to deepen”. These are also the steps for making real an innovative catalytic process. The development of a commercially successful process is in any case a scientific as well a technical triumph. The journey of an idea, from its birth at the level of discovery up to the start-up of a commercial prototype, is a sequence of steps of increasing difficulty to be overcome, that can assume different names, like discovery, explorative phase, intensive phase, predevelopment, development and, eventually, venture and commercial application [24, 25, 26]. Even in a continuum, the R&D activities, can be grouped into two basic periods, the “explorative and definition phase” and the “intensive and development phase”, being the former already oriented, but still looking for a general definition of the process, and the latter strictly finalized to achievement of the complete technology know-how.

2.1. The explorative and definition phase Beyond the role of fundamental research of providing the tools for any knowledge advancement, all finaljuly - august №4

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ized industrial R&D projects face the “explorative and definition phase”, that includes all actions aimed at assessing: • the technical feasibility of the innovation: thermodynamic constraints control, reaction scheme sequence, potential catalyst hypothesizing, preparing, characterizing and screening, process conditions exploration, level of novelty evaluation (how many wheels have been reinvented!) are the most typical activities, • the economical potential which implies mass and heat balances, some conceptual process design hypothesis, and a rough prediction of production cost and some economical indexes, and • the “social” feasibility which will verify the environmental impact of the process, of the products of intermediates etc. Even if there are not technical short-stoppers, before entering the following and expensive intensive and development phase, it is necessary to verify the new process expected economics. If the new process does not appear convenient (even assuming “dream” performances), only a very strong strategic motivation (of a company or a government through the research financing institutions) can leave alive the project. A recent example of this type is the intense current activity on hydrogen, on which an economical return is expected well beyond the pure financial requirements, but it is pursuing a strategic perspective of enormous impact. In the past the Fischer-Tropsch synthesis allowed South African government the production of fuels and chemicals from coal during the “apartheid” embargo. The early definition of some “Criteria of Success” and the control on the achievement of intermediate milestones is fundamental in order to select the best projects. The techno-economical evaluation of the process must be anticipated as much as possible and repeated in any case of important “good or bad news” from Research. Bad projects’ killing is absolutely necessary for strengthening the good ones, but remains a very difficult task! In this phase of development of catalytic processes the critical step is the identification/availability of a suitable catalyst. Catalysis was practiced long before it was recognized as a scientific discipline, but today “on-purpose” catalyst design is scientifically supported by the development of sophisticated and effective physico-chemical investigations at micro and macro level of the catalyst characteristics, old and new in situ-operando powerful techniques, microkinetics and mechanistic simulations, catalyst modeling. Electronic structure methods based on density functional theory №4 july - august

(DFT) have reached a level of sophistication where they can be used to describe complete catalytic reactions on transition metals giving an unprecedented insight into molecular catalysis, and allowing looking better to the origin of the catalytic activity of a metal in terms of its electronic structure [27]. The objective remains the synergy of three vertexes of the triangle: how the catalyst has been prepared (Material Science); how it actually “looks” (Physicochemical Characterization and Surface Science); how it performs (Catalyst testing). As concerns equipment, the explorative phase is certainly carried out at “laboratory level” in bench scale units. The experimental check in laboratory of the feasibility is generally limited to verifying the chemical feasibility of the process, i.e. only the chemical factors (such as reactivity, yields, selection of the catalyst active components, etc.) are examined, independently from the size and therefore directly scalable, if phenomena dependant upon size were not present. In a first phase all “physical” factors (those connected with fluid motion, material and energy transport limitations etc) are frequently disregarded, but never forgotten. This very initial phase of experiments gives a preliminary indication on how to address the research in the future. Experimentally typical operation relies on small reactors (glass, quartz, or even metallic) with few cc or even hundreds of milligrams of catalyst generally in powder and granulates, not in the final shape. In this phase the set up of reliable analytical methods remains fundamental, as well for having satisfactory material balances (in this phase the error on balances and reproducibility might not exceed 3-5%) as well for identifying main byproducts: the devil is in the details! Recently new “high throughput” techniques have been developed and it is possible to operate in parallel several reaction chambers and testing in short time several catalyst formulations or various operating conditions (temperature, space velocity, concentrations). Of course to a high availability of information must be associated a high capacity of handling them, and not only with computers! For liquid phase systems, autoclaves (generally in batch) are the most used equipment.

2.2. The intensive and development phase In order to be exploited at industrial level, findings of the explorative phase have to be tested and applied in larger dimensions. This work process is called scale-up.


Scale-up is defined as an increase in size, quantity, or activity according to a fixed scale or proportion. The intensive and development phase is finalized to the acquisition of the technology complete knowhow. The development of a catalytic industrial process is a complex interdisciplinary activity finalized to transform an idea into innovation getting and integrating all theoretical and experimental information on the catalyst, on the reaction, on the reactor, and on the entire process. The keyword in this phase of development is “optimization” of: the catalyst formulation, its performances, and operating conditions, of the best reactor configuration, products purification, and eventually of the process flowsheet including energy and raw materials consumption, investment costs, safety, environmental constraints and impact, and controllability among other aspects. The industrial development of a catalytic process is based on experimental studies. Haber and Bosch received the Nobel Prize for their basic studies on the ammonia synthesis, but the production process was based on over 20,000 catalytic tests carried out by Mittasch. Indeed the basis of intensive research is the collection of absolutely reliable experimental data. As concerns equipment, the intensive-development phase is carried out on bench scale plants at laboratory level, on pilot plants, on process demonstration units (PDU); typically reactor size increases from grams to kilos and tons of catalyst. Scale-up prepares the following commercial phase, which means the translation to a commercial scale of the experience gained since the lab experiments. Scale-up, therefore, beyond the technical approach, covers several aspects of the coming commercial activity, including product development and market studies. In the intensive research phase, even at laboratory level, experiments and equipment must be designed bearing already in mind the full scale plant: the first step of scale-up is therefore scale-down the hypothesized problems of commercial unit bringing them to the small lab scale where all information needed can be collected and modeled effectively. Scale-up from small scale studies based on making “the toy bigger”, could be a very misleading concept. The breakdown into simpler subsystems has some limits, since it increases the risk of missing some key factor in the investigation or of attributing to the system some effects due to the small scale.

Oversimplifying, three experimental approaches are possible: i) bench scale, where the mechanisms that are independent of size (thermodynamics, kinetics, chemical mechanisms) are studied, ii) mock-up (cold models), in order to analyze separately the physical mechanisms sensitive to size (fluid dynamics), and iii) finally pilot plants or even demonstration units which permit a simultaneous analysis of physical and chemical mechanisms, and of their interaction. The process design and optimization is as much important as the catalyst optimization. The reactor conceptual choice and design together with the chemical reaction engineering and the design of all unit operations of the process (including feed and product separation-purification) makes real the possibility of developing a new catalytic technology. Chemical reaction engineering (CRE) is concerned with the rational design and/or analysis of performance of chemical reactors, the heart of any chemical process [28, 29]. Design of chemical reactors is also at the forefront of new chemical technologies. Improvements in the reactor usually have enormous impact on upstream and downstream separation processes. The process engineers will have to translate discoveries and knowledge of the reaction, transferred by the researchers, into a new process and must supply everything else is needed to define the Process Design Package. Assumptions must be made about which types of process units should be used, how those process units will be interconnected and what temperatures, pressures and process flow rates will be required: this activity is named “conceptual design”. Conceptual design can be approached at different levels during the development of a chemical process. The main key to the successful design of a new process is the continuous transfer of information between researchers and engineers, particularly the feedback of engineers to researchers, identifying critical points and addressing further research to clarify them. At the moment in which process development begins, the reaction has been tested in laboratory reactors, a catalyst is available, even if it will not be the final one, possible by-products and a plausible stoichiometry have been determined. A range of possible operating variables (temperature, pressure, space velocity) and the reaction phase have been determined, too. The engineering of catalytic reactors has benefited from this increased understanding of reaction mechanisms; mass and heat transfer phenomena in july - august №4

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catalyst pores, pellets, and beads; and mathematical modeling of catalytic processes and flow motion through computational fluid dynamics (CFD). New catalysts with tailor-made molecular designs are already playing important roles in advancing industrial technologies. At the same time, new ideas emerging from research promise breakthroughs that may make industry more efficient, safer, and more environmentally friendly. Techno-economical evaluations [30, 31] for the assessment of the feasibility of commercial opportunities for the new catalytic process are fundamental in this phase and drive many technological choices. Favorable economics will give the green light to the continuation of the project. Even in the phase of advanced development the search for new solutions and breakthroughs has to continue: experience says that sometime the exploration of parameters and variable outside the ranges assumed as optimal may open the doors to a breakthrough. Scale up from laboratory scale to industrial scale in one step is rarely feasible. Pilot plants or even PDU allow to study the entire process, including the purification sections, and to get large amount of product for evaluation by potential clients (internal or external). At this demonstration scale there is also the experimental check of by-products that sometime changing from once-through systems (like in laboratory) to recycle systems may unexpectedly build up. The accepted calculated risk determines the extent of homology and then the scale up ratio (the relationship between the size of the foreseen next scale unit and the size of the current experimental one) that is required in the intermediate step. Due to the high cost of pilot plants, there is great interest in moving in one step from bench scale to, at least, a process demonstration unit (PDU) to be used as a reference for larger future installations. There are no general rules for scale up ratios. Typical values based on experience are reported in the Table 3. Higher scale up ratios, at an acceptable level of risk, can be achieved only when marginal modifications to an existing technology (incremental research) are planned or extensive experience exists on similar systems or when a fundamental approach is possible to both chemical and engineering problems. There are examples of successful scale up ratios from bench scale to PDU or semi-commercial scale plants exceeding 100,000 or even 500,000 or difficulties met with a factor of only 5. №4 july - august

Table 3. Typical scaling-up ratios from lab to industrial plants Systems

Lab to pilot

Pilot to ind.

gaseous

500-1000

200-1000

reag. gas-prod.liq.

200-500

100-500

Reag. liq./gas-prod.liq

100-500

100-200

A very important aspect of the development of catalytic processes is the scale-up of the catalyst production from the few grams typical of lab preparation to the tons needed by commercial units. Catalyst production is a real, complex chemical process handling generally solids that requires the same attention as that paid to the reaction.

2.3. Projects survival and success rate The idyllic picture appearing up to now is not always or entirely true. Commercializing a new catalytic process is capital-intensive, and as long as 10 to 15 years may be required from the discovery of a viable catalyst for a new process to commercial plant start-up. Most new processes are complex and large-scale pilot plants or PDU are required to collect the data needed to design and build safe, clean, and efficient commercial plants. Development can easily cost tens of millions of dollars, and the new commercial plant may cost hundreds of millions of dollars. Thus developing breakthrough catalyst systems is risky, time-consuming and costly [32]. Experience indicates that only a small number of innovative ideas complete their journey up to commercial implementation. First of all, it is not an easy task to overcome all the technical difficulties and achieve superior products/processes. Furthermore in almost all cases the initial scheme will require additional treatments, purifications, recycles and so on not included in the original design. But even in the case of technical success, other hurdles make a selection among R&D projects: during the several years required by the process development, the economic scenario can change substantially (in the last 30 years the oil price has been subjected to sudden ups and downs) or the company strategy can change, the results can arrive too early (market not yet mature) or too late (someone else has arrived


first) and, in any case, how big should be the contemplated advantage of choosing the new technology at the eyes of the investor or financing bank for prevailing over a referenced competing product/process? 10% or 20% or 30% or even higher? What is the breakeven between potential benefits and risk? One of the key factors will be the attitude of the companies regard to innovation. As a consequence R&D projects undergo very considerable “attrition”, like entering in a virtual funnel from which just a few come out. According to some industrial experience, about 80% of the projects at the discovery phase reach the definition phase, less than 50% initiate the development phase, and only 20% of them survive up to the serious evaluation for a venture phase. A different picture is given by another source [33] according to which 1 to 3% of ideas for a new process at the early research stage reaches commercialization. Projects at the development stage have a probability of about 10 to 25%, and at the pilot plant stage of 40 to 60%. Of course, the success rate for marginal modifications of existing technologies will be higher than that of completely new processes.

2.4. Multidisciplinarity mandates integration “No organ of the human body can claim the right to consider itself more important than the other ones and refuse to cooperate with them, otherwise the entire body will die.” (Menenius Agrippa, 494 b.c.). As we have seen, the handling of the complexity of the phenomena involved in catalysis, in catalyst and catalytic processes development, involves skills coming from many complementary, each one developing independently its own progress and advancing towards a very sophisticated level of specialization. Catalysis needs integration and “bridging the gaps” [34]: gaps between catalyst preparation and performances, between model catalyst and working catalyst, between laboratory and industrial conditions, between reactor engineering and catalyst formulation, between electronic structure calculations at molecular level and experimental results, and not to be forgotten, between business and science. Successful catalytic processes development requires bringing in a common culture members from different disciplines such as materials and surface science, solid state physics and chemistry, organometallic chemistry, chemical kinetics, reaction and reactor engineering. Integration is achieved bearing in mind that the development activity is not a relay race and the project

has not to pass from one competence to the next like the baton from one racer to the other, but all skills have to work together synergistically from the lab level up to the start-up of the commercial unit, with a continuous feedback of information. Integration is an unavoidable necessity that should not be felt by the individuals as an ethical duty or a management imposition, but as an intrinsic cultural attitude. Management has the responsibility of the correct involvement of the broad spectrum of specialist skills and of making available the complete view of the total problem under study. A form of integration is also the collaborations of industrial research with universities and scientific institutes that promotes new roads for future technology developments. These collaborations not only enlarge the cultural basis of the projects, but educate synergistically industrial researchers to apply new scientific concepts in their “real-world” and academic researchers to introduce “real problems” in their world. It is fundamental the integration inside the company between the organization functions in order to preserve the warm attention of the business to R&D projects in order to accelerate the time to market. Commercial R&D in industrial catalysis, as in other fields, is typically a high-risk investment with a deferred payoff. Any R&D project has to pass through a period of negative cash-flow (the so-called Valley of Death) before the income starts to recover the expenses. It is wrong to view R&D projects as a cost since, as with other high-risk investments, returns can be extremely attractive. Joint development and joint ventures with other companies to share risk, and select and evaluate high-quality methods offers a higher chance of success. The value-creating potential for investment in industrial catalysis depends on technical opportunity and commercial opportunity. When both are aligned within the company, prospects are excellent for coming true the sentence “Science to Dollars” [H. Topsøe in 34]. By experience, a strong internal sponsorship and commitment is a necessary catalyst for success!

Conclusions The process industry faces challenges requiring innovative efforts. Catalysis and the related disciplines are continuously evolving from the point of view of both the proposition of new technological topics and the availability of new scientific methodologies that, through a deeper understanding of elementary steps, allow a conceptual design of the catalyst at molecular level and its engineering systems. Technological chaljuly - august №4

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lenges for industrial catalysis are the keys for creating new opportunities for knowledge progress. Catalysis allows better utilization of fossil resources through selectivity control: in the future, selectivity to form the desired product without the formation of byproducts will be one of the major research challenges. Our understanding of the molecular ingredients of selectivity needs to be improved. New synthetic methods of catalyst preparation are needed for precise control of size, structure, location of additives and location of catalyst particles on supports. Characterization of the catalysts under reaction conditions is essential as the catalyst restructures in the presence of the reactant mixture [63]. During the coming decades, oil will still be the main source of energy [64] and will supply a large share of the fuel required by industry and virtually all the fuel required for transport. Catalytic technologies are expected to allow the “white refineries” with complete conversion of the bottom of the barrel and the exploitation of unconventional heavy oils such as Venezuelan and Canadian resources. During the last decade, proven world gas reserves increased considerably, exceeding oil reserves in barrel of oil equivalent. Furthermore enormous methane reserves are trapped as hydrates at the oceans rims. Additionally to the use for primary energy generation, Natural Gas is expected to be more and more exploited through its conversion in catalytic industrial processes to produce liquid transportation fuels and intermediates for the chemical industry. There is a growing interest for the use of NGL, the wet fraction of NG, as clean feedstock for high quality fuel components and for chemicals. Hydrogen is candidate to become a major vector of energy in the future, but it must be associayted with the use of renewable energy sources or the CO2 sequestration if it is produced from fossil fuels Biomass has the potential for contributing to provide alternative feed for producing energetic vectors via catalytic processes, but it has to be considered the competition with the food for human beings. Catalytic processes intensification through integration of unit operations in reactor engineering and advanced catalysis like in membrane reactors [65], catalytic distillation [66, 67], micro-channel reactors [68] etc. offers potential breakthrough benefits increasing product yields and selectivities, energy efficiency by improving heat and mass transfer performance, shrinking processing equipment cost-effective creation of new products by enabling optimal processing №4 july - august

conditions not possible with conventional hardware. Given the combined challenges of achieving environmental protection at all stages of production, use, and disposal of chemicals and of using at improved efficiency new sources of raw material feedstocks, industry needs efforts from fundamental and practical approach to catalysis. As to individuals, a major challenge is to smooth the barrier between science and technology. Without the Fundamental Science, all technological progresses are marginal, as well without the technological implementation, cultural and financial efforts in scientific progress become meaningless for the social benefits. Chemistry and Catalysis play a key role in this aspect and the relevant technologies impregnate all our daily actions. Charles Darwin said “In the long history of humankind (and animal kingdom too), those who learned to collaborate and improvise most effectively prevailed”. It is a very good suggestion.

Acknowledgements I wish to express my appreciation to the many colleagues that with their creativity, inventiveness and firm will, have spent their best efforts to generate and develop the ideas I described here.

References 1 Bible, Genesis 9, 20 2 Arnold J-P. (2005) Origin and History of Beer and Brewing: From Prehistoric Times to the Beginning of Brewing Science and Technology. ISBN 0-96620841-2 3 Dautzenberg F. M., Angevine P. J. (2004). Encouraging innovation in catalysis Cat. Today, 93-95, 3-16 4 SRI (Stanford Research Institute) (1996) Catalysts Process Economics Program Report 153A. A multiclient study on catalyst market 5 Marcilly C. (2003), Present status and future trends in catalysis for refining and petrochemicals, J. Cat. 216, 1-2, 47-62 6 TCGR (The Catalyst Group Resources) (2004): Intelligence Report - Business shifts in Global Catalytic Process Industries 2003-2009 7 Rabo J.A. (1993) New Frontiers in Catalysis Proc. 10th Int. Cong. on Catalysis, Budapest 19-24 July 1992 Ed. Guczi, et al... Elsevier 8 Rifkin J. (2002) The Hydrogen Economy Penguin Putnam Inc. 9 Holmgren J. et al. (2007) A New Development


in Renewable Fuels: Green Diesel NPRA Annual Meeting March 18-20, 2007 San Antonio, TX Paper AM-07-10 10 Federchimica (2004) Chemical Industry in numbers. Responsible Care Program 11 Sanfilippo D., Miracca I., DiGirolamo M. (2005) Engineering alkanes to olefins and higher value chemicals in Sustainable Strategies for up-grading Natural Gas: Fundamentals, Challenges and Opportunities. Derouane E. et al. Eds. NATO ASI Math., Phys. and Chem. 191, 217-247 (Springer) 12 Rabo J.A., Schoonover M.W. (2001) Early discoveries in zeolite chemistry and catalysis at Union Carbide, and follow-up in industrial catalysis. Appl. Cat. A Gen. 222, 1-2, 261-275 13 Kaminsky W. (2000) Polymerization catalysis, Cat. Today 62, 1, 23-34 doi:10.1016/S09205861(00)00406-5 14 Sanfilippo D., Miracca I. (2006) Dehydrogenation of paraffins: synergies between catalyst design and reactor engineering Cat. Today 111, 1-2, 133-139 15 Guczi L., Van Santen R-A., Sarma K-V. (1996) Low-Temperature Coupling of Methane Catal. Rev.-Sci. Eng. 38, 249 16 Rostrup-Nielsen J. (2005) Natural Gas: Fuel or Feedstock in Sustainable Strategies for up-grading Natural Gas: Fundamentals, Challenges and Opportunities. Derouane et al. Eds. NATO ASI Mathematics, Physics and Chemistry, 191, 3-24 (Springer) 17 Rostrup-Nielsen J., Alstrup I. (1999) Innovation and science in the process industry Steam reforming and hydrogenolysis Cat. Today 53, 3, 311-316 18 Lange J-P. (2005) Economics of alkane conversion: Economic guidelines and techno-economical evaluation of alkane conversion processes. In Sustainable Strategies for up-grading Natural Gas: Fundamentals, Challenges and Opportunities. Derouane et al. Eds. NATO ASI Mathematics, Physics and Chemistry 191, 51-83 (Springer) 19 Blaser H-U. (2000) Heterogeneous catalysis for fine chemicals production Cat. Today 60, 3-4 161165 20 Cornils B., Herrmann W-A. (2003) Concepts in homogeneous catalysis: the industrial view J. Cat. 216, 1-2, 23-31 21 Centi G., Ciambelli P., Perathoner S., Russo P. (2002) Environmental catalysis: trends and outlook. Cat. Today 75, 1-4, 3-15 22 EIRMA (European Industrial Research Management Association) (1998) Creativity and Innovativeness. Workshop Report IX EIRMA 34, Rue de Bassano Paris

23 Sanfilippo D. (1997) The catalytic process from laboratory to the industrial plant, CatToday 34, 1-2, 259-557 24 Roussel P-A., Saad K-N., Erikson T-J. (1991) Third Generation R&D, Arthur D. Little Inc. Harvard Business School Press, Boston 25 Hoyle W. (1997), Pilot Plants and Scale-up of Chemical Processes Special Publication No. 195. The Royal Society of Chemistry 26 Nauman B-E. (2002), Chemical Reactor Design, Optimization, and Scaleup, McGraw-Hill, 27 Nørskov J-K., Hammer B. (2000) Theoretical surface science and catalysis, calculations and concepts Adv. Cat. 45, 71-129 28 Schmidt L-D. (1998) The engineering of chemical reactions. Oxford University Press New York Oxford 29 Missen R-W., Mims C-A., Saville B-A. (1999) Introduction To Chemical Reaction Engineering And Kinetics, John Wiley & Sons, Inc. 30 Newnan D-G. (2004) Engineering Economic Analysis. Oxford University Press, Inc. - New York (USA) 31 Behrens W., Hawranek P-M. (1995). Manual for the Preparation of Industrial Feasibility Studies UNIDO, Vienna ISBN 92-1-106269-1; 32 Boer F-P. (2005) Research is an investment, not an expense Appl. Cat. A: Gen. 280, 1, 3-15 33 Douglas J-M. (1988) Conceptual design of Chemical Processes. McGraw-Hill 34 Clausen B. (2006) Frontiers in Catalysis: A Molecular View of Industrial Catalysis CatToday 111, 1-2 35 Somorjai G-A., McCrea K. (2001) Roadmap for catalysis science in the 21st century: a personal view of building the future on past and present accomplishments Appl. Cat. A: Gen., 222, 1-2, 3-18 36 EIA U.S. DOE, Annual Energy Outlook 2010, Washington, DC 20585 ,www.eia.doe.gov/oiaf/aeo/, April 2010 37 Dalmon J-A. et al. (2007) Oxidation in catalytic membrane reactors Appl. Cat. A: Gen. 325, 2, 198-204 38 Harmsen G.J., (2007) Reactive distillation: The front-runner of industrial process intensification A full review of commercial applications, research, scale-up, design and operation, Chem. Eng. Proc. 46, 9, 774-780 39 Miracca I., Judzis A. Jr., Sahayi N., Sanfilippo D. (2008) Catalytic Distillation in Heterog. Cat. Handbook, 2nd Ed.Vol. 4- 10.6, 2188-2198 - G. Ertl, H. Knotzinger, F. Schueth, J. Weitkamp Ed. Wiley-VCH 40 Mazanec T. (2007) High Intensity Olefin Production in Microchannel Reactors AIChE Meeting, Houston, TX April july - august №4

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УДК 340.1(574)

THE KAZAKH BIY COURTS WERE KEPT AND REMAINED IN THE MEMORY OF GENERATIONS AS INDEPENDENT, PROFESSIONAL AND WISE JUSTICE S.Z. Zimanov The academician of the National Academy of sciences of the Republic of Kazakhstan

Представлены основные результаты исследования степного права. Суд биев воплотил в себя ценности народной демократии и основывался на понятии справедливости, как ведущем принципе правосудия. 18

Дала (қыр) құқығын зерттеудің негізгі нәтижелері көрсетілген. Билер соты өз бойына халықтық демократия құндылықтарын жинақтаған және әділеттіліктің басты қағидасы ретіндегі әділдік ұғымына негізделген.

Keywords: biy’s court, nomadic civilization, Kazakh law There are events, dates and people in the history of each nation. The subsequent generations respect and are proud of them, remember them as remarkable and their major events, spiritual rise in their lives. There are such phenomena, as institutional structures and establishments, which are kept strictly and seize memory and minds of new generations, that they have civilized meaning or even universal value. They are kept and live in their ideas as orientation to the future and a heritage having lasting value. Such memorable historical phenomen are the Kazakh legal proceedings - biy courts, formed within the nomadic society of the Turkic Kazakhs who lived during the century which was made and received the name “The Golden Age” of justice. When it stopped to exist as “The Golden Age” of justice, it remained as an everlasting torch in national memory. №4 july - august

The court as the public body was and remained the criterion and symbol of authority and management at all times and epoch by which features were judged about the authority, about its adherence to democracy and interests of people. As a rule, such representation prevails at those layers of the population which concern to objects -to the participants of proceeding who feels the attitude and difficulty of judicial authority towards themselves and those who stand on top of authority and creates court doesn’t have such feelings. The authority and prestigiousness of the biy legal proceedings had sank in the layers of the history long ago, had became the property of compassion and dream of all society, including dominating layers in present conditions of Kazakhstan. It is paradoxical, but the fact speaking much about general value of justice of biys. It is necessary to make the initial clause and to define the concept “about biy courts in the nomadic society of the Kazakhs here”. In this case there is no speech about desire of absolutization of a society of


the Kazakh nomads, especially about its isolated consideration in separation from its settled and city part or connections with it. The matter is, it is important to note, allocate, that biy justice in the valuable immanent status could be formed, developed and affirmed only in the environment and masses of classical nomadic part of the Kazakh society occupying the huge space of the central - Asian contingent and making overwhelming majority of the population of the Steppe territory. The city and agricultural culture interspersed and in the most part took the style of management and norm of behaviour from neighbouring settled regions and countries influenced the Kazakh nomadic society very little, on the contrary, made its and strengthening in the certain degree.

The biy courts was an ideal for modern statespersons of the Republic D.A.Kunaev, who governed the Kazakh Republic during the Soviet authority for a long time, was the member of the Political bureau of the Central Committee of the CPSU and the First Secretary of the Central Committee of the Communist Party of Kazakhstan. He remained the active member of leading communist party, which ideology has not been compatible with the worship for the medieval history especially oppressed people, at the same time he had special respect to one of the legendary Kazakh biys- judges Tole biy. He had three photographs on the working table of his house; they were photos of Dimash Akhmetovich, Tole biy (in the center) and his wife Zuhra Sharipovna [1]. The first and present President of the independent Republic of Kazakhstan (since 1990) N.A.Nazarbaev, the former First Secretary of the Central Committee of the Communist Party of the Kazakh SSR, named the ancient Kazakh biys — judges as “Multiksiz adil, ot auyzdy, oraq tildi sheshender” — “Leaders with oratorical gift and feeling of faultless validity” in one of official speeches. N.A.Nazarbaev spoke about three well-knownbiys, who lived in the XVII - XVIII centuries and whose names were connected to echoes of “The Golden Age” of justice in the Steppe territory, Tole biy, Kazybek biy, Aiteke biy the following: “Barsha qazaq balasy attaryn ardaqtap, aitqandaryn jattaghan osy ush babamyzdyng el aldyndaghy engbegine, qkhalyq qamyn jegen adal isine soz jetkizip bagha bery qiyno” Ush danagoidyn onegeli omiri, el qamyn jegen adal engbegi, top bastaghan kosemdigi, ot auyzdy, oraq tildi sheshendigi, m,ultiksiz adildigi jonindegi aitar angime az ernes” — “They became a lasting symbol of unity

for the Kazakhs, their passionate speeches seized minds of descendants, as sayings from sacred books”. It is possible to speak much about the famous lives of these three great people, about their acts for the sake of honour, advantage and sacred glory of people, about their natural leaders’ talent, oratorical gift, faultless validity”[2]. A biy as a judge, biy courts as the judicial authority has being continued till nowadays, in conditions of modern Kazakhstan, to personify and are officially used as worthy imitations of model of professionalism and the fair attitude towards the using of judicial function. Therefore, the court with participation of the jurymen, entered in the Republic as the idea for maintenance of the maximal validity during the settlement of the most complex jurisdiction of criminal cases has been called “biyler alqasy” the translation is “the board of biys”. The memory to great biys-judges - to courts of biys is shown here, for whom the independence, professionalism, philosophical reflection, speaking, limiting validity and honesty were the basic principles of their judicial vital activity. Despite of centuries which separate present generation from “The Golden Age” of biy justice and from its last separate representatives who reminded of it, in spite of the fact, that from that time socially political environment has radically changed which product it was and to which it served, despite of it and nowadays discussions about wide introduction of a heritage of biy courts or nomination of biys, as judges in judicial system in the Republic flash from time to time. In this case it is not important for us how far it is comprehensible or unacceptable. It is important that the biy justice does not only continue to be star twilight in the historical memory of people, but also has been its valuable orientation in a policy of democratization of the judicial organization in the Kazakh state.

Research information about courts of biys in the nomadic society of the Kazakhs The human history is rich with paradoxes and contradictions and it happens quite often which are born in their disorder and there are the phenomena representing pieces, the oases of universal value at first sight poorly accessible to habitually logic explanation. The special authority of biy judicial system in the Kazakh nomadic society was such puzzle - an innovation for understanding, which was considered as backward from the positions of the western civilization. Almost all foreigners from the European countries, irrespective of july - august №4

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their status and the purpose of stay in the Steppe territory, named the Kazakhs of nomads of the XII-XIX of centuries as nomads by the way of life, “half-civilized’ by the ways of survival in natural sphere, “patriarchal” by the patrimonial division which has kept in the population and management, “violent” by upholding interests and freedom of development of huge pasturable space, “powerless’ by absence of open division of the population on citizenship and governors which was habitual for the West at that times. Management and authority in the big and small nomadic collectives had dual attributes. On the one hand, they belonged to those who had the greatest influence and respect by age, experience, natural insight in conditions of corporate -public social institutes, and on the other hand, belonged to those who were allocated by the property status on a background enough appreciable social stratification of the population on rich and poor. Remoteness of the Kazakh nomadic society from the centres of Asian and western civilizations, it’s fogged and “nomadic backwardness” served as the reason of late attention to it on the part of the Eurasian educated elite. The first foreign and especially Russian researchers came to the Kazakh steppe only in the beginning of XIX century. They have seen and have opened special institutes and the phenomena representing general values, such, as adherence to eloquence and sophistication, as a reigning cult of literature and the legality, formed in the life and in public consciousness in the internal organization and structure of the Kazakh society. A.I.Levshin, the largest Russian scientist - orientalist who visited the Kazakh steppe in 20th years of the XIX century with the research purpose, got world (global) glory for fundamental works about Kazakhs, wrote: The most intellectual Kirghizs of the Younger horde spoke that there was time when our people lived in peace, there was time when we had order, there were laws and justice. That was the Golden Age which they remember with sighs, it was the reign of the well-known khan Tauke who, if to trust legends, was really the genius in own way, and in Cossack annals should stand alongside with Solons and Likurg. Having pacified worrying clans and generations, he has not only entered the management and order, but has also given them many laws. The Kazakhs of the senior and Middle hordes assert that their national laws are much ancient than Tauke khan’s”[3]. The A.I.Levshin’s statement was not a note marked slightly. One of fundamental issues and features of the history of the internal formation of the Kazakh nomadic society which was seized and expressed, making №4 july - august

and explaining of its former unity and force in the law. Its world, formation and order in a society have been based, as told by the author about laws and justice. They are the basis of that Golden Age of the Kazakh ground. From his and other authors, his contemporaries’ statement we consider that the first role was played by justice in all that ordered public processes. And not general justice, but the justice sent by biys, especially allocated from the society as a social group of professionals, who were worthy and adequate to their epoch. The speech about this will be a bit later. Such paramount role of justice of the Kazakhs has been connected not only by the medieval nomadic society management. It was reduced basically to the sanction of disputes and conflicts arising in it. That was usual, historical phenomenon distributed everywhere. That was necessary to rise up the justice to a national rating of the Golden Age, that it has seized not ordinary attributes and the essence, especially allocating it among known and traditional establishments similar to it. These strict requirements were characteristic to the justice performed by biys during an epoch of their eminence as independent, wise national judges. It is necessary to note one more valuable place in A.I.Levshin’s statements. He mentioned that “the wisdom” Kazakhs connect “the Golden Age” with the period of reign of khan Tauke in the Kazakh society (last quarter of the XVIII century). Not casually, that national memory has kept and allocates that period. Namely during the reign of khan Tauke, there was another - an official recognition of the leading role of biys in the political life of the Kazakh society in infringement of century tradition when khan supporters were always chinghizids- sultans. Tauke khan applying for all Kazakh throne in difficult years for the society and distributing the influence on all three Kazakh juzes, according to sources, in the activity has decided to lean entirely on biys in the activity, periodically convoked congresses of biys, considered the major questions internal and foreign policy there. It was not the beginning of process, which was the result of development of the previous epoch. The merit of Tauke khan consists that he has selected and used force and authority of the justice given by biys in realization of the state policy, which was influential in administrative and managerial system in the society. If to reply the question in what period of the history of Kazakhstan the formation of biy justice, it is enough to answer or note that it has been formed several centries and it became the phenomenon of the national scale only during the period of reign of khan Tauke. The nomadic way of life was powerful


preservative of its valuable figures some of the representatives of “The Golden Age” of justice were kept, have lived until the beginning of the XX century. Such cases were judged and found out how they managed to keep the maintenance and legality in a nomadic society in the previous centuries and what the powerful factor in preservation was and maintenance of unity of the Kazakh nomads scattered and stretched on huge steppe open spaces of central Asian contingent. Professor Grigoriev V.V., the known Russian orientalist was the most competent scientist of the second half of the XIX century while giving the description of the life of the Kazakh nomads and their internal structure. His advantage was explained, first, by his direct and deep knowledge of the language and life of the population of the Steppe territory, its cognitive ability and style of the researcher. About ten years heading the governmental administration on management of the Western part of Kazakhstan (from the middle of XIX century), he was in close contact to the Kazakh society, was in the near and far auls, nomadic encampments mainly on patrimonial division. In addition to all that, Professor Grigoriev V.V. used the documentsin imperial offices archival and current materials about the Kazakhs. In one of the works devoted to the comparative analysis of the history of the east Turkic people, having in view the Kazakh society, he wrote: “Nomadic way of” life could not be considered ordinarily incompatible with some significant economic and intellectual development. But it is hardly thorough”[4]. Confirming this idea he further said: “В пастушеских еще обществах возникает иногда, как видим у киргизов (казахов— С.З.) такое превосходное судопроизводство и такие порядки следственного и судебного процесса, каким могут позавидовать многие издавна цивилизовавшиеся народы”. “In nomadic societies sometimes still arises as it is seen at the Kirghiz (the Kazakhs S.Z.) such excellent legal proceedings and such orders of investigation and litigation to what civilized people can envy”[5]. The other Russian scientist Slovohodov L.A., the lawyer by education expressed also about biy courts and the Kazakh right “Jarghi”, who worked in the imperial administration in Kazakhstan for many years. He studied and knew the Kazakh language, spoke it excellently, and was personally familiar with many representatives of local nobility. He wrote the special work about the justice in the society of nomadic Kazakhs [6]. He considered the biy court as “original” and “national” because it was close and useful to people, carried not accusatory, only competitive character. “Legal proceedings of the Kirghiz (the Kazakhs S.Z.) people were

democratic, publicly, simple and short. People have developed original, but quite clear structure of litigations, avoiding so harmful bureaucratic elements during the long period of time”. Justice in the Steppe territory, which was performed by biys, were loved by people and therefore it was the valid judicial authority [7].

Biy courts in the estimation of figures of national culture of the XIX and the beginning of XX centuries Formation of national intelligence in the Steppe territory concerns to the second half of the XIX and to the beginning of the XX centuries. It is closely connected to Russia and Russian culture. Certainly, there were only a few educated people earlier especially in the settled centres, who had got education basically in the neighbouring Muslim centres, serving as letter writers, translators and spiritual instructors at khans, sultans and clan governors, taught their children in the initial Arabian letter. The most gifts went to the scientific centres of the East. Actually, the Kazakh national intelligency which has been brought up on the advanced traditions of the secular Russian European culture, though very few by number, they were the new educated layer in the society. Irrespective of, where they served, they were closely connected to the life of nomads and in many cases always carried in the essence their image of life, sights and thoughts. Some of them rose up to the level of known scientists and thinkers. Descriptions, statements, and researches of representatives of the national intelligency, as experts, direct representatives of all ordinary and not ordinary, small and real in the organization of a corporate, common-clanic, individual way of life of the Kazakh nomads are of great value. The main thing was that they saw and lived in that economic, social, spiritual environment, characteristic for the Kazakh nomadic society with all its inherent attributes and models of selforganizing. Until the beginning of the XX century the ancient biy courts and norms of Kazakh law “Jarghi” were still kept isolated, and especially in distant and far areas of steppe where transformations did not reach yet though they felt their influence to some extent. Moreover, the historical memory of people about the “The Golden Age” of justice has not been covered with stratifications yet. The heritage of the oustanding Kazakh scientist Chokan Valihanov (1835-1865) is especially valuable, who was characterized by contemporaries as “the ingenious researcher of the East”, “a meteor flown on july - august №4

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a field of oriental studies”. In the connection to the Russian Government reforming, he asked the bodies of imperial authority, persuaded them not to make the full replacement of old biy courts of the Steppe by a new colonial judicial system, for the sake of calmness and internal well-being of the Kazakh society, together with the interests of the colonial autocracy. In the note “Court in the ancient national form”, he wrote the following: “Biy is not selected and affirmed formally. The value of them is based on fair authority, which is got by them in the same way as in European poets, scientists and lawyers. Shakespeare and Goethe are considered as great poets by all, but the genius of them is based not on decrees of the governments and not on formal elections of people”; ... only deep knowledge of the judicial customs, connected with oratory, gave the Kirghiz (Kazakhs) this honorary title ; the biy courts were made verbally, publicly and in all cases supposed legal profession. They were in such respect that did not demand and does not demand till now any disciplinary actions; the main advantage of biy courts, in our opinion, consists in absence of formalities and any official routine. The value of biy is based on authority and knowledge which is the patent for judiciary practice”[8]. The great Kazakh poet Abai Kunanbaev’s (18451904) products are known in all corners of the world nowadays, and whose sculptural monument has been established on one of the central streets of Moscow, wrote about biys and biy courts in the years of “The Golden Age” of justice, the following: Bui bilik degen bizding qazaq ishinde arbir sailaghan kisining qolynan kele bermeidi...Ras, buringhy bizding ata-babalarymyzdyng bul zamandaghylardan bilimi, kutimi, sypaiylyghy, tazalyghy tomen bolghan, biraq bul zamandaghylardan artyq ей minezi bar eken... 01 eki minezi qaisy desek, aueli-ol zamanda el bassy, top bassy degen kisiler bolady eken. kosh qondy bolsa, day —janjaldy bolsa, bulik bolsa solarda bolady eken. Ozge qara jurt, jaqsy-jaman ozderining sharuasymen jure beredi eken. 01 el bassy, top bassylary qalqi bitirse qalyqta ony synamaq, birden birge jugirmek bolmaidy eken”[9]. - “We had an opportunity to be convinced of uselessness of biy- judges elections in each volost. Not everyone could manage to make a justice. ... Yes, [former biys] certainly conceded to present people in erudition, courtesy, tidiness and neatness. But they possessed two advantages which we do not have at present ... What qualities do we speak about? There were people which were called “el bassy”, “top bassy” during ancient times. They solved disputes, operated life of the society, and simple peo№4 july - august

ple were engaged in the affairs. It was not accepted to challenge the decision of “el bassy”, “top bassy” or to run from one to another [10]. Alikhan Bokeikhanov was very educated intellectual, the large representative of political liberation movement in Kazakhstan at the beginnings of the XX century, repeatedly expressed that the biy courts has gone down to history of the Kazakh people as “national court” by the fact and form, and that the policy of colonial authorities connected to replacement of it by other courts which is impossible to consider as the successful decision. One of his articles was entitled “Qazaqtyng biyining опту bolek” — “The Kazakh biys had special place” [11]. There has been told much by him. The oustanding Kazakh educator and publicist Ahmet Baitursynov wrote and proved about radical distinctions in orientation and functions of the new appointed biys-judges becoming a part of machinery of state of the imperial government, and biy- judges who had made “The Golden Age” of justice in the history of the Kazakh people which separate representatives have lived till the new time. He named one of his articles as “Burynghy adil biyler” - “The last biys were the symbol of valid justice”. He wrote that “Xalukh sot degenimiz qazaqtyng ghadetindegi qaghidalar bjiynsha aitylatughyn bulik. Burynghy adil biylarding qolyndaghy bulik qazaqtyng neshe turli dertyn jazatyghyn jaqsy dari edi, bugingi aran biylaerding qolynda dari bolmaq tugil, ou bolyp jughyp tur” — “The national court is that which was earlier. The justice was based on the Kazakh common- legal establishments at those times. It was in the hands of biys who was devoted to validity, gave the prescription of medicine from all troubles, but now it is in the hands of modern state biys who will give poison instead of medicine”[12].

The Soviet authority could not eliminate “The Golden Age” of the Kazakh justice from the historical memory of people It is amazingly and at the same time paradoxical that during the Soviet epoch, despite of the official ideology of denying something valuable in pre soviet history of the Kazakhs and others similar to them colonial people, for instance the notion about biys and biy court were something as about high, truly national establishment lived and continued to live in the memory of nation and in sights of authoritative intellectuals of the Kazakh people. Sometimes it was splashed out outside in their statements. As it was dangerous and the author could be accused in “political unreliability”, in


“nationalism”, they expressed the opinions frequently indirectly gave them the description “strange”, but which has the connection with described cases and events. So, K.I.Satpaev the geologist and the intellectual, scientist with world acceptance, in one of his early works, devoted to the legendary biy and the governor of the Nogai-Kazakh Horde of the XVII century Edige biy, he gave the characteristic of him by the expression distributed in people “Khanda qyruq kisining aqyly bar6 biyde qyryq kisining ary, bilimi bar” — “Khan has the wisdom of forty men, and biy has- conscience and knowledge of forty men”. By his words in a society of nomadic Kazakhs “There was always more respect to biys than to khans”[13]. The writer with a world name and scientist Auezov M.O. has devoted a big article to “The dialogue of biys”“Biylar aitysy” in which responded about them enthusiastically and showed several examples of participations of biys in competitions, their eloquence and art of proving which helped them to solveprincipal conflicts adequately [14]. The academician of the national academy of sciences, the big expert of the ancient and medieval history of the Kazakh people Margulan A.K. wrote, that many well-known biys, the experts of the antiquity and literature of the Kazakh people were invited from time to time to Omsk, which was one of the centers of colonial administration of the Kazakh Steppe in the XIX century. In his opinion “Munda keletin adamdar kobinese qalykhtyng rukhani tirshiligin, onyng sheziresin, ertegijyrlaryn biletin kileng sheshen biyler, quylma aqyndar, ataqty kuishiler bolghan” — “There were mainly invited biys, silver-tongued orators, poets improvisators, musicians, experts on the life, spiritual culture, the history and folklore of people”[15].

There was spoken openly about the justice of biys during the independent years of the Republic After disintegration of the Soviet empire and declaration of the state independence of Kazakhstan there have been talked openly about biys and biy courts and about system of Kazakh law Jarghi”, inseparable from each-other as historical values. As the respect of the generations there was constructed a large monument of 4 metres height from the granite in Astana, the capital of the republic in front of the building of the Supreme Court of the Republic.This monument was devoted to three oustanding biy-judges who live in the second half of the XVII and the first half of the

XIX centuries, Tole biy, Kazybek biy, Aiteke biy. They are represented orientally sitting next to each other, staring to the distant space.The historical place — the steppe natural boundary in the southern Kazakhstan oblast was declared as the historical memorial park “Ordabassy”, the translation is “the khan horde” by the government because the congresses of biys from three juzes were held there several times. On one of high hills of park there was established high-altitude monument. If you want to rise up to the top of the hill you can reach there by the terraced ladder which leads from the root of the hill. The Presidents of three neighbouring Turkic Republics - Kazakhstan, Uzbekistan and Kirghizia took place in opening ceremony on May, 1993. The president of the Republic N.A. Nazarbayev has told in the speech, that “The biys became a lasting symbol of unity for the Kazakhs; their passionate speeches have seized minds of descendants, as sayings from sacred books. It is impossible to overestimate their importance in our history, their historical merits before the Kazakh people” [16]. The high estimation of merits of biy-judges before the history of people was given in works of scientists, art workers, including the works of the prominent Kazakh writers known for the historical novels. The author of the novels “Blood and sweat” and the “Duty”, which were translated into several languages and became the best seller in the countries of Europe, has entitled one of his articles as “Biy-judges and orators”. It was Abdijamal Nurpeissov, who wrote: “В самом деле, с годами я, все чаще оглядывая мысленно иные пласты веков казахской истории, все более поражаюсь тому огромному доверию, к той опоре его на мудрость и высоту духа, что были присущи Высоким Его Сыновьям. И эта опора никогда не подводила мой народ. И не потому ли находим мы ныне в истории тысячелетнего института биев - ораторов тому немало удивительных примеров”. “Really, after several years, turning out to other layers of centuries of the Kazakh history, I realized more and more that there was a huge trust and support on wisdom and height of spirit that were inherent to its Big Sons. Moreover, that support will never betray my people. Therefore we find a lot of surprising examples in the history of thousand-year institute of biy-orators nowadays”[17]. Another oustanding writer Kekilbaev Abish, the author of several highly artistic and philosophically constrained historical novels and stories, has entitled one of the his articles devoted to biy -judges and orators “Esimderidynie turghansha urpaqtardung jadynda saqtalady” — “ Their names will be kept in memory july - august №4

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of generations until there is a world”.He wrote about them the following: “Nurlary eki duniede birdie shalqyp, jandary jannattyng torinde uemdengen, esimderi dunie turgansha urpaqtardung jadynda turatynyn jaryqtarymyzdy osynau dunie turgansha kueli ghumarattaghy buyrmas mekenderine qaita jalghastyrghanymyzgha tauba dep tyrmyn” - “ we must thank our destiny that there has stepped the day when our great sons which light lit up the two worlds - terrestrial and heavenly, and their names are included into the annals of eternity, could return them in their places - in the sacred palaces of national consciousness”[18]. For years of independence of the Republic only 16 difficult years, there was a real splash of articles and works, more descriptive, about the Kazakh biyjudges, who were in the memory of generations and known by its folklore, hand-written and narrative sources. The serious research works have also begun. Offered multivolume “the ancient world of the Kazakh law” — “qazaqtyng ata zangdary” is the first fundamental work of searches on this way. It applies to be the intermediate final research opening open spaces for new researches, and at the same time it is the fascinating documentary material about biy- judges, their wisdom and art of the decision of disputed conflicts. The work deserves and it should enter the annals of universal culture by its right. Sometimes it could be difficult to explain, especially when there has run a lot of time between the subject of an explanation and explainer. It is difficult to believe in that, which was trusted by many people, including authorities, when the whole epoch of conscious denying has run between real historical events and cognitive activity of the new time, behind which was well organized wall from ideologists. In these conditions, the reality is seemed as mirage, and mirage as reality. That happened to the Kazakh legal system “ Jarghi” with central figures of biy courts. They played the central, regulating and uniting role in a life of the nomadic society of the Kazakhs for the last centuries. It has been appreciated by the young generations of nomads and post nomads and estimated as the scientific idea. Nowadays it is considered as the mysterious epoch-making phenomenon representing universal value.

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References 1. Dautov S. Abyz, ili uvazhenie r minuvshemu / “Vechernii Almaty”. 2006. August, 24. 2. Nazarbaev N.A. Five yeas of independence. Almaty. 1996. P. 153. 3. Levshin A.I. The description the KirghizCossack or the Kirghiz-Kaisats of hordes and steppes. SPb. 1832. Part III. P.169. 4. Grigoriev V.V. About Scythian people saks. Almaty. 1998. P. 43. 5. Ibid. P. 44. 6. Slovokhodov L.A. National court of a common law the Kirghiz of the Small horde / Works of the Orenburg scientific archival commission. V. XV. Orenburg. 1905. 7. Ibid. P.. 80, 81. 8. Valikhanov Ch.Ch. The collected works. V. I. Alma-Ata. 1985. P. 494-523. 9. Kunanbaev A. Eki tomdyk shigarmalarynyn tolyk zhinagu. V. 2. Almaty. 1997. P. 16-17. 10. Kunanbaev A. The book of words. Almaty. 1992. P. 18-19. 11. The newspaper “Kazakh”. 1914. № 50. 12. Baitursynov A. Zhana nizam. Almaty. P. 14. 13. Satpaev K.I. “Er Edige”. М. 1927. 14. Auezov M. Adebiet tarikhy. A. 1991. 188191. 15. Margulan О. Ezhelgi zhyr, anyzdar. А. 1995, 234-235. 16. Nazarbaev N.A. Five years of independence. - А. 1996. P. 153. 17. Nurpeisov A.K. The ideas caused by acts of ancestors. In book Aiteke biy. А. 1998. P.49-54. 18. Kekilbaev A. “Egemen Kazakhstan” // 22 Mausym 1999.


УДК 665.612.2

CONVERSION OF REAL ASSOCIATED GASES BY CARBON DIOXIDE OVER THE KMR-8 СATALYST Sh. S. Itkulova D.V. Sokolsky Institute of Organic Catalysis & Electrochemistry; 142, Kunaev str., Almaty, 050010, Republic Kazakhstan; Fax: (7) 727 - 2915722; e-mail: [email protected]

Новый цеолит-содержащий нанесенный катализатор исследован в реакции взаимодействия между диоксидом углерода и реальным попутным нефтяным газом (ПНГ) при варьировании температуры 350-800oC. Показано, что катализатор проявляет высокую активность в риформинге ПНГ диоксидом углерода. При 800oC фракция углеводородов C2+ полностью конвертируется, степень конверсии метана - 91.7, а диоксида углерода - 90.2%. Основным продуктом реакции при 800oC является синтез-газ (смесь оксида углерода и водорода) с соотношением H2/CO=1.3. Также образуется вода и небольшие количества (2.8%) кислородсодержащих продуктов (в основном уксусная кислота) при T ≤ 600oC. Кроме активности и селективности еще одним из достоинств синтезированного катализатора является его устойчивость к коксообразованию. Бұл жұмыста цеолитке қондырылған жаңа катализатор синтезделінді. Катализаторда әр түрлі процесс температурасы (350-800oC) алмастыру кезінде ілеспе газ және көміртек диоксидінің конверсиясы зерттелді. Катализатордің активтілігі ілеспе газ және көміртек диоксиді әрекеттескенде синтез-газ, соның ішінде сутегі көбірек мөлшерде түзілген жағдайда көрінетіңдігі анықталынды. C2+ фракция 800оС температурада толық конверсияға түскенде Н2/ СО қатынасы 1.3 құрайды.

Abstract The new supported zeolite-containing catalyst has been investigated in the reaction of interaction between carbon dioxide and real associated petroleum gases (APG) at varying experiment temperature within a range of 350-800oC. It has been shown that the catalyst performs the high activity in carbon dioxide reforming of APG. At 800oC, the C2+ hydrocarbon fraction is completely converted, degree of methane conversion is 91.7 and carbon dioxide conversion is 90.2%. The main product of reaction is synthesis-gas (mix of carbon oxide and hydrogen) with a ratio of H2/ CO=1.3 at 800oC. Also water and small amount (2.8%)

of oxygenates (basically acetic acid) are produced at T ≤ 600oC. One of the advantages of the synthesized catalyst in addition to its activity and selectivity is its resistance to coke formation. Key words: zeolite-containing catalyst, associated gases, carbon dioxide, synthesis-gas

Introduction Associated petroleum gas (APG) is still burned in Kazakhstan. Kazakhstan ranks the fifth place on amount of burned APG. Information on total amount of burned gases in Kazakhstan is not complete and has an inconsistent character. In 2008 according to july - august №4

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the official data the gross output was 33.5 bln. m3 at that volume of burned associated gases was decreased to 1.8 bln. m3 [1]. From 25 to 1000 m3 of associated gases is extracted at producing 1 ton of oil at the Kazakhstans’ oil and oil-gas condensate fields. In a best case they are squeezed into oil reservoir. This approach does not solve the problem of associated gases utilization. Moreover as a rule it leads to raising the gas amount at the following oil extraction and increasing a cost of re-squeezing. At APG combustion, the high value hydrocarbon raw material is aimlessly burned that is accompanied with carbon dioxide and hazardous sulfur and nitrogen oxides formation. Carbon dioxide among these anthropogenic gases is a main greenhouse gas. The amount of carbon dioxide formed exceeds twice the amount of burned fuel. Obviously that burning of APG is unacceptable from a point of view of environment protection and resource-saving. One of decisions of this problem is creation of infrastructure for APG collection, transportation, purification, separation, and squeezing into a main pipe line that requires the huge investments [2]. Other way is processing of APG into motor fuel, methanol, and other high value products directly at the oil fields [2-4]. The light hydrocarbons in composition of APG can be converted into liquid products by so called GTL process (Gas-To-Liquid) [4].Also they can be a source for hydrogen production [5]. The GTL process has been considered as a clean and alternative process in an environmental respect. By GTL the light hydrocarbons are converted into syngas. Syngas, a mixture of H2 and CO is a major feedstock for methanol, ammonia and Fischer–Tropsch (F–T) synthesis. There are three main catalytic ways for syngas production from hydrocarbon feed with involving: 1) water - steam reforming (equation 1), 2) half oxygen - partial oxidation (equation 2); and 3) carbon dioxide - dry reforming (equation 3). The last one attracts an interest because of allows utilizing greenhouse gases – methane and carbon dioxide with producing syngas with a ratio of Н2/СО = 1 [6-10]. (eq.1) CH4 + H2O → CO + 3H2 (eq.2) CH4+1/2O2 → CO + 2H2 (eq.3) CH4 + CO2 → 2CO + 2H2 The aim of this study was the development and test of the new catalyst – KMR-8 for converting the real associated gases by involving into process carbon dioxide (dry reforming) with producing syngas. №4 july - august

Experimental The catalyst – KMR-8 with total metal content - 5 weight % supported on alumina promoted with zeolite has been synthesized and tested in conversion of real associated gases (APG). The process was carried out in a flow quartz reactor at atmospheric pressure and varying experiment temperature from 300 to 800oC. Space velocity (S.V.) was 1500 hr-1. The catalyst loading was 10-30 mL. Ratio of CO2:APG in dry reforming was constant - 1:1. The composition of associated gases extracted from one of oil wells of the West Kazakhstan is presented in Table 1. Table 1. Hydrocarbon composition of real associated gas extracted from one of oil wells of the West Kazakhstan Hydrocarbons

С4

С5

С6

С7

Content, 52.1 20.1 14.0 8.1 vol. %

4.4

1.1

0.2

С1

С2

С3

The set for APG conversion was combined with gas chromatographs (GC) equipped with thermal conductivity detector for on-line analysis of Н2, Ar, СО, СН4, О2, СО2 (columns: molecular sieves and activated coal) and flame-ionization detector (FID) for on-line analysis of hydrocarbons (column: modified alumina). Liquid phase was collected in a special cooled trap (separator) and then analyzed by GC equipped with FID on columns: Carbowax/Carbopak and Poropak N, as well as by IR-spectroscopy. The carbon formation was controlled by thermogravimetric analysis (TGA), thermo-programmed reduction (TPR) and electron microscopy. The catalyst was studied with using BET, IR-spectroscopy and electron microscopy.

Results and discussion The conversion of hydrocarbons at dry reforming of APG (interaction with carbon dioxide) over the KMR-8 catalyst already runs at 350оС. With increase in temperature from 350 to 800оС the conversion degree raises for all hydrocarbons (C1-C7) and carbon dioxide as it is shown in Figure 1. It needs to note that then higher the molecular weight of hydrocarbon then less temperature of its complete conversion. Thus, 100% conversion of C7 is occurred at 350оС, С6 - 550оС, С5 - 600оС, С4 - 700оС, С3 - 750оС, and С2 - 800оС (Figure 1).


Figure 1. Effect of temperature on conversion degree of hydrocarbons and CO2 at dry reforming of associated gases over the KMR-8 catalyst

At raising temperature from 350 to 800оС, methane conversion increased from 20.9 to 91.7%, and СО2 conversion – from 51.6 to 90.2% (Table 2). Table2. Effect of temperature on dry reforming of associated gases over the KMR-8 catalyst (APG / СО2=1/1, Р= 1 atm, space velocity – 1500 hr-1) Degree of conversion (K), % Т, С о

Н2/СО

КС1

КС2+

KСО2

350

20.9

51.2

51.6

1.9

400

28.7

56.6

67.2

1.2

450

32.5

59.0

68.0

1.1

500

43.6

74.2

67.2

0.8

550

47.8

86.6

68.5

0.9

The main product of APG conversion by carbon dioxide is syngas. At lower temperatures – 350-450oC syngas is reached with hydrogen, because production of carbon oxide is started later. With following increasing temperature to 550oC the yield of carbon oxide is surpassed hydrogen and Н2/СО 97

69.7

1.0

2.8

800

91.7

100

90.2

1.3

not observed

The catalyst demonstrates the high resistance to coke formation. By electron microscope it was shown that the catalyst keeps its high dispersed state after reaction. july - august №4

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Conclusions The KMR-8 catalyst performs the high activity in dry reforming of associated gases. The conversion degree XCH4 = 91.7% and XCO2 ~ 90.2%. Syngas produced has an appropriate ratio for Fisher-Tropsch synthesis - Н2/ СО=1.3. The advantages of the synthesized catalyst also are the stability and resistance to coke formation. The catalyst worked with the stable activity during all period of its exploitation (more than 50 hours). The catalyst can be recommended for the industrial application to produce syngas from APG. In whole,

References

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1. Smirnov S. // J. Expert Kazakhstan. 2009. №10 (265). 2. Solovyanov А.А., Andreeva N.N., Kryukov V.A., Lyats K.G. // Strategy of using associated petroleum gases in Russian Federation. Moscow, Newspaper “Quorum”. 2008. P. 320. 3. Trimm, D. // In Sustainable Strategies for Upgrading of Natural Gas: Fundamentals, Challenges, and Opportunities. Under edition of E.G. Derouane, V. Parmon, F. Lemos, and F.R. Ribeiro. Springer. 2005. V. 191. P. 125 and P. 137. 4. Wilhelm, D.J., Simbeck, D.R., Karp, A.D., Dickenson, R.L. // Journal Fuel Processing Technology. 2001. V. 71. P.139. 5. Krylov O.V. // J. Catalysis in chemical and petrochemical industry. 2007. N 2. P. 13. 6. Arutyunov V.S., Lapidus A.L. // Rus. Chem. J. (J. of Mendeleev Rus. Chem. Soc.). 2003. V. XLVII. №2. P. 23. 7. Ashcroft, A. T., Cheetham, A. K., Green, M. L., and Vernon, P. D. F. // Nature. 1991. V. 352. P. 225. 8. Chang J.-S., Park S.-E., Yoo J.W., and Park J.-N. // J. Catal. 2000. V. 195. P. 1. 9. Ruckenstein E., and Wang H. Y. // J Catal. 2002. V. 205. P. 289. 10. Xu, B. Q., and Sachtler,W. M. H. // J. Catal. 1998. V. 180. P. 198.

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the introduction of the technology of APG utilization into practice will promote the mitigation of carbon dioxide emissions.

Acknowledgement Author is grateful to academician of NAS of RK, Prof. G.D. Zakumbaeva for her assistance and consultation at implementing this study. The special thanks to the Laboratory of physico-chemical study of catalysts of IOCE for carrying out the catalysts investigation.


УДК 547.979.7+0.26+541.427.49

СOMPLEX FORMATION OF METALPHAEOPHYTINS WITH POLY-4-VINYLPYRIDINE HYDROGEL E.A. Bekturov, 2 Zh.K. Korganbayeva, T.K. Jumadilov 1 Institute of High Technologies, Almaty, Kazakhstan 2 A.B. Bekturov Institute of Chemical Sciences, Almaty, Kazakhstan e-mail: [email protected] 1 2

Изучено комплексообразование между различными металфеофитинами и П4ВП методами электронной и γ-резонансной спектроскопиии. Электронды және γ-резонансты спектроскопия әдістерімен әр түрлі металдыфеофитиндер мен П4ВП гидрогелі арасындағы комплекстердің түзілуі қарастырылған. 29

Abstract Сomplex formation between various metal phaeophytins and poly-4-vinylpyridine was investigated by UV-VIS and γ-resonance spectroscopy. Keywords: Porphyrins, phaeophytin, polymer-metalphaeophytin, cobaltphaeophytin, nickelphaeophytin Introduction Porphyrins attract great attention due to their important role in nature processes and wide range of application: medicine, catalysis, electronics etc. This paper is dedicated to investigation of porphyrins obtained from Kazakhstan plant sources and its complex formation with metal ions and poly-4vinylpyridinе (P4VPy) by UV-VIS and Messbauer spectroscopy [1, 2]. Experimental Swelling coefficients were measured by weight method. Messbauer spectras were obtained by spectrometer SM-2201. UV VIS spectra were measured by JASCO UV-VIS 7580. Results and discussions Swelling kinetics of poly-4-vinylpyridine in etha-

nol and ethanol solution of phaeophytin was studied (Figure l). Equilibrium value of swelling coefficient K of P4VPy is lower in presence of porphyrin due to binding of components. At Figure 2, contraction of P4VPy gel in presence of different metal phaeophytins is shown. It can be seen that contraction is more expressed in case of nickel phaeoplytin. It is a result of coordination complex formation of P4VPy with metal ions. UV VIS spectra of porphyrin containing systems in dimethyl formamide (DMF) are presented at Figure 3. At complex formation of phaeophytin with metal ions, where metal ions occupy centre of coordinating plain N4 with formation MN4 coordination pack it is observed batachrome shift and intensity of absorption band decrease in long wave field [3, 4]. These systems were studied by γ-resonance spectroscopy. Messbauer spectra of ironphaeophytin shows presence of Fe(III) with next parameters: Isomeric shift Is=0.43 (mm/s), quadrapole splintering Qs=0.47 (mm/s). At Figure 4, γ-resonance spectra of polymer-metalphaeophtin complex are shown. These spectra demonstrate the presence of two components with next parameters: 1. Is=0.39(mm/s), Qs=0,74 (mm/s), S=96% 2. Is=0,57(mm/s), Qs=1,13(mm/s), S=4% july - august №4


Fig. 1. Swelling kinetics of P4VPy gel in ethanol (1) and in ethanol solutions of phaeophytin (2)

Fig. 2. Swelling kinetics of P4VPy gel in ethanol solutions of iron phaeophytin (1), cobaltphaeophytin (2) and nickelphaeophytin (3) Fig. 3. UV-VIS spectra in DMF: Php (СPhp = 10-4 mоl/l) (1), Php (СPhp = 1,5•10-5 mоl/l) (2), P4VPy-NiPhp (СPhp = 10-5 mоl/l ) (3), P4VPy-СоPhp (4)

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The first component have the value of Is close to value for iron-phaephytun but the quadrapole splintering have the remarkably higher value, showing the coordination between polymer and metalporphyrin. This interaction is verified also by presence of second com-

ponent with high spin state iron (II). So, coordination of polymer with metalphaeophytin is accompanied with partial metal reduction. Sharp change of quadrapole splintering Qs from 0,47 to 0,74 mm/s shows the remarkable change of

Fig.4. Messbauer spectra of P4VPy – FePhp system №4 july - august


Fig.5. Scheme of complex formation of metalphaeophytin with P4VPy the surrounding symmetry of iron ions. It may be the result of changing complex’s structure with release of iron ions from the plain of porphyrin macro cycle (Figure 5). Catalytic properties of P4VPy hydrogel-metalporphyrin complex in model decarboxilation reaction of sorrel acid were studied [5-7]. From Figure 6, where expense of permanganat plotted versus time, it can be seen, that more active catalyst is polymer complex of cobaltphaeophytin (curve 1)

Fig. 6. Decarboxilation reaction of sorrel acid in absence (3) and presence of polymermetalphaeophytin complex: gP4VPy-CoPhp(1), gP4VPy-NiPhp (2)

References 1. Аskarov K.F., Berezin B.D., Yevstigneeva R.P. et al., M. Nayka. – 1985. p.7-13. 2. Kadish K.M., Smith K.M., Guilard R. The Porphyrin Handbook. - SanDiego: Academic Press, – 1999. – 145p. 3. Nikolaeva O.I., Ageeva T.A., Koifman O.I. Synthesis of Physiologically Active Polymers Containing Covalently Bounded Porphyrins And Their Metallocomplexes. II International Conference on Porphyrins and Phtalocyanines. – Kyoto, Japan. – 2002. – P. 506. 4. Mamardashwili N.J., Golubchikov O.A., Usp. Chim. 2001, V.70. №7. p. 656-686. 5. Scheer H., Katz J. in Porphyrins and metalloporphyrins / Ed. K.M. Smith. Amsterdam. etc.: Elsevier. – 1975. – p. 399 – 524. 6. Syrbu C.A., Ageeva T.A., Semeikin А.С., Коifman О.U. Izv. Acad. nauk. – 2007. – №4. – p.. 680-700. 7. Коifman О.U, Ageeva T.A. / Ros. Chem.J. – 2004. – V.48, №4. – p. 140.

Conclusion Complex formation between poly-4-vinylpyrridine and different metal phaeophytins was studied by methods of UV-VIS and γ-resonance spectroscopy. It was shown that in these system complexes are forming due to coordination of nitrogen atom of P4VPy with metal ion of metalphaeophytins. july - august №4

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Дмитрий Мурзин, профессор университета Або Академи города Турку в Финляндии, автор более 450 статей по катализу и химической технологии, член редколлегий ряда международных журналов (Химическая промышленность сегодня, Катализ в промышленности, Applied Catalysis A.; International Journal of Chemical Engineering), вице-президент Европейской федерации каталитических обществ, академик Societas Scientiarum Fennica

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Как Вы приняли решение стать химиком, кто повлиял на Вас? В моей семье никто к химии отношения не имел, моя мама – филолог, заканчивала МГУ, а папа после окончания ГИТИСа работал актером в Москве в театре Гоголя, а затем был долгое время главным администратором театра Эстрады. Мне же химия понравилась, наверное, в классе 6 или 7, а уже в 9-м я принял решение, что хочу поступать в МХТИ им.Д.И. Менделеева. Сначала это была вечерняя химическая школа, а потом уже и сам институт (ныне Российский химико-технологический университет), инженерный химико-технологический факультет. Как проявился интерес к катализу? В каком -то смысле это дело случая. Я заканчивал кафедру химии и технологии органического синтеза, занимался, будучи студентом, научной работой, которая была связана с синтезом фосфорилированных карбаматов, и думал продолжить эту тему в аспирантуре. Несмотря на то, что я получал Ленинскую стипендию, в середине 80-х годов были определенные проблемы оставлять москвичей в аспирантуре на кафедре, и заведующий кафедрой профессор А.Л. Чимишкян предложил распределиться в НИФХИ им. Л.Я. Карпова, за что я ему очень благодарен. Так я попал в лабораторию выдающегося ученого М.И. Темкина, с которым мне посчастливилось проработать почти 6 лет. Как Вы оказались в Финляндии? Как Вам нравится работать тут? Так получилось, что в 92-94 годах я стажировался во Франции и Финляндии, после чего работал на №4 july - august

крупнейшей химической фирме БАСФ в Германии и России, не прерывая контактов с университетом Або Академи, будучи там доцентом. В 2000 году мой предшественник, заведующий кафедрой химической технологии, уходил на пенсию, и освободилась вакансия. В результате конкурса, где экспертами, оценивающими кандидатов, выступали несколько зарубежных ученых, был сделан выбор в мою пользу. Думаю, что опыт работы в промышленности помог в этом. Какой круг задач и проблем Вы сейчас изучаете? Кафедра, на которой я работаю, довольна большая по скандинавским меркам, более 50 человек. Поскольку Финляндия маленькая страна с довольно развитой промышленностью и устоявшимися тесными связями науки и промышленности, мы занимаемся довольно широким кругов вопросов, относящихся к химической технологией. С методологической точки зрения они связаны с гетерогенным катализом, прикладной кинетикой и моделированием реакторов. Что касается реакций, то за последние 10 лет очень четко проявился сдвиг тематики от нефтехимии к переработки возобнавляемого сырья. Вы много работаете с промышленностью, расскажите немного о том, насколько это важно для вашей исследовательской работы? Это исключительно важно для кафедры. В Финляндии четкое понимание, что основная задача науки, которая здесь делается в университетах, - получение нового знания, даже если проект финансируется полностью или частично промышленностью. Мы ста-


раемся следовать принципам моего учителя профессора Темкина, всегда изучавшего фундаментальные вопросы на примере промышленно важных реакций. Так что сначала прорабатывается вопрос возможного патентирования, а потом обязательно мы публикуем статьи в международных журналах. Какие из исследований, которые Вы вели, наиболее Вам дороги? Тут мне сложно что-то выделить одно. Все, чем занимаюсь, разжигает любопытство и доставляет удовольствие, когда находишь ответы на те вопросы, которые казались неразрешимыми. Что в Вашей работе нравится больше всего? Опять же сложно выделить что-то одно. Нравится, например, наблюдать профессиональный рост аспирантов, их взросление, как профессиональное, так и человеческое.

Расскажите, пожалуйста, в чем секрет успешного руководства большим научным коллективом? Мне кажется, надо по мере возможности собирать в группу талантливую молодежь, учить ее и давать возможность научиться как у более старших коллег, так и друг у друга. И последний вопрос. Какие у Вас связи с Центральной Азией, и Казахстаном в частности? Первая всесоюзная конференция, в которой я участвовал, была в 1986 году в Алма-Ате. Она стала толчком к многолетнему сотрудничеству с Сапаром Конуспаевым, ныне профессором; сотрудничеству, которое продолжается и по сей день. Я очень высоко ценю работы школы Д.В. Сокольского в области катализа, надеюсь, что казахстанские ученые будут и впредь продолжать эти славные научные традиции.

Dmitry Murzin, the professor of Åbo Akademi University, Turku, Finland, the author more than 450 papers on catalysis and chemical technologies, a member of editorial boards of some international journals (Khimicheskaya promyshlennost segodnya, Catalysis in Industry, Applied Catalysis A.; International Journal of Chemical Engineering), vice-president of the European federation of Catalytic societies, the academician of Societas Scientiarum Fennica

How you have made a decision to become the chemist, who has affected you? In my family nobody had attitudes to chemistry, my mother - the philologist, finished the Moscow State University, and father after graduated from GITIS worked as the actor in Moscow at Gogol's theatre, and then he was long time the chief manager of Estrada theatre. The chemistry has liked me, probably, in the 6 or 7 class, and already in the 9th class I have made a decision, that I wish to enter into D.I. Mendeleev Mos-

cow Chemical and Technological Institute. First it was the evening chemical school, and then already the Institute (nowadays the Russian Chemical and Technological University), engineering chemical-technological faculty. How there was an interest to catalysis? It was casual. I finished faculty of chemistry and technology of organic synthesis, carried out scientific work which has been connected with synthesis of phosphorjuly - august №4

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ylated carbamates, and wished to continue this theme in postgraduate study. In spite of the fact that I received the Lenin grant, in the middle of 80th years there were certain problems to leave Muscovites in postgraduate study on faculty. Professor A.L. Chimishkyan, head of faculty, has suggested me to be distributed into L.Ya. Karpov Institute of Physical Chemistry, for what I am very grateful. So I have got into laboratory of outstanding scientist M.I. Temkin with which to me has had the luck to work almost 6 years. How you have arrived to Finland? How you like to work here? In 92-94 years I trained in France and Finland, and then worked in the largest chemical firm BASF in Germany and Russia, not interrupting contacts with Åbo Akademi University, being there the senior lecturer. In 2000 my predecessor head of the faculty of chemical technology has retired, therefore a vacancy was released. As a result of competition where the experts estimating candidates were some foreign scientists, the choice in my advantage has been made. I think that the operational experience in the industry has helped me.

It is exclusively important for faculty. In Finland there is a precise understanding that the primary goal of a science which here is done at Universities is a reception of new knowledge even if the project is financed in full or in part by the industry. We try to follow principles of my teacher professor Temkin which always studied fundamental questions on an example of industrially important reactions. So, the question of possible patenting in start is studied, and then necessarily we publish papers in the international magazines. What researches which you conducted are most important you? Here it is difficult me to allocate something one. Everything, than I am engaged, kindles curiosity and gives pleasure, when you find answers to those questions which seem insoluble. What it is pleasant you in your work most of all? It is difficult to allocate something one. I like observe, for example, professional growth of post-graduate students, their growth both professional, and human.

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What questions and problems you study nowadays? The faculty, on which I work, is big on the Scandinavian measures, more than 50 people. As Finland is the small country with the developed industry and the settled close communications of science and industry, we are engaged wide circles of the questions concerning chemical technology. From the methodological point of view they are connected with heterogeneous catalysis, applied kinetics and modelling of reactors. As to reactions for last 10 years shift of subjects from petrochemistry to processing of renewable raw material was very precisely showed. You work with the industry much; tell a little about that, how much it is important for your research work?

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Please, tell about a secret of successful management of big scientific personnel? I think, it is necessary to collect talented youth in group, learn them and give opportunity to learn as from more senior colleagues, and each other. And last question. What you have communications with the Central Asia, and Kazakhstan in particular? The first all-Union conference in which I participated was in 1986 in Alma-Ata. It became a push to long-term cooperation with Sapar Konuspaev, nowadays the professor. This cooperation proceeds till now. I appreciate works of D.V. Sokolsky School in the field of catalysis and hope that Kazakhstan scientists will continue these nice scientific traditions.


Галина Ксандопуло, профессор, д.х.н., работает в Национальном научноисследовательском центре «Демокритос» в Афинах, в Греции, автор более 200 публикаций по катализу, процессам горения в твердой фазе, керамическим материалам, член редколлегий ряда международных журналов, консультант Европейской Комиссии.

Не могли бы Вы рассказать о научном центре, в котором Вы работаете? Научно-исследовательский центр «Демокритос» был образован в 1958 году и в начале назывался Научный центр ядерных исследований «Демокритос». Целью Центра было использование ядерной энергии в мирных целях. Впервые в истории Греции из-за рубежа были приглашены греческие ученые, которые провели инфраструктурирование и организацию широкомасштабных исследований в Греции. «Демокритос» стал первым многонаправленным Центром в стране. В 1985 году Центр был переименован и получил современное название. Центр относится к Министерству образования, Генеральному Секретариату по Науке и Технологии. В настоящее время в самом большом научном центре Греции работает 850 человек, 650 из кото-

рых научные сотрудники. «Демокритос» состоит из восьми институтов: Институт Ядерной Физики, Инсти-

тут Ядерной Технологии и Радиационной защиты, Институт Материаловедения, Институт Телекоммуникаций и Информатики, Институт Микроэлектроники, Институт Физической Химии, Институт Биологии и Институт Радио-Фармацевтики. Области исследований в этих институтах связаны с ядерной физикой, энергией – охраной окружающей среды, нанотехнологиями, микросистемами, интегрированными телекоммуникациями и информационными технологиями, современными технологиями по изучению археологических объектов и античных скульптур, контролем загрязнения окружающей среды, ядерными технологиями и радиационной защитой, технологиями ускорителей и детекторных устройств, созданием и характеристикой новых материалов, биоактивными молекулами, биотехнологиями. По данным 2009 года 30% от всей научной продукции центров Греции приходится на «Демокритос». В 2009 году учеными Центра «Демокритос» было опубликовано 557 статей в международных журналах, а за 10 последних лет – 4000. В 2009 году было опубликовано 437 тезисов конференций и более 5000 за последние 10 лет. Работы Центра были цитируемы за последние 10 лет 35000 раз. Каждый год Центр организует около 30 конференций, симпозиумов, около 20 кандидатов, 20 мастеров, 35 дипломников защищаются каждый год в «Демокритосе». В «Демокритос» есть технологический центр «Лефкипос», с помощью которого за последние 5 лет было организовано 22 компании. Каждый год «Демокритос» организует летние школы, которые посещают около 250 студентов различных институтов страны. Они прослушивают курс july - august №4

35


Мои родители и дочка лекций по различным дисциплинам, читаемых ведущими специалистами Центра о новейших достижениях в науке.

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Почему Вы решили стать ученым? Не могли бы Вы рассказать о своей учебной и научной судьбе? Решение стать химиком возникло очень рано, в детские годы. Дело в том, что моя мама Иванкова А.И. замечательный химик – аналитик однажды взяла меня в свою лабораторию Института Минерального Сырья (КазИМС). Мне тогда было 5 лет, но я до сих пор помню волшебный мир разноцветных растворов в колбах, приборов, ученых в белых халатах. Все это было завораживающим и прочно осело в моей памяти. Мой папа Ксандопуло Г.И. теперь академик, известный ученый в области горения, в 60-х годах только начинал свой путь и я видела его интенсивно работающим дома каждый день. Я могу сказать, что пример моих родителей, их увлеченность химией, глубокое уважение к ним определило мое реше-

Сотрудники СВС катализаторов лаборатории ИПГ в 1988г. №4 july - august

ние стать ученым. Очень значительным влиянием на это решение оказала также возможность общаться со знаменитыми, талантливыми учеными, которые часто бывали у нас дома, когда приезжали на конференции в Алма-Ату, такими как Нобелевским лауреатом Семеновым Н.Н., академиком Зельдовичем Я.Б., Эмануэлем Н.М., Ениколоповым Н.С., Кондратьевым В.Н., Тальрозе В.Л., Берлиным А.А., профессорами Потехиным Г.С., Гершензоном Ю.М., Веденеевым В.Л. и Мержановым А.Г. Их работы были событиями в науке. Я восхищалась этими людьми и мой папа сказал очень мудрые слова: «Если хочешь быть среди таких интересных людей, ты должна учиться и много работать, накапливать знания. Людям нравится общаться с равными». Это были ключевые слова, определившие мое будущее. Я поступила в школу № 39 с химическим уклоном с очень хорошими учителями, затем на химический факультет КазГУ им. С.М. Кирова (теперь альФараби), где в то время работали талантливые преподаватели: Усанович М.И., Сокольский Д.В., Миркин В.А., Соломин А.В., Зоров Г.В., Стрельцова В.М., Фасман А.Б., Друзь В.А. и многие другие. Я помню их фразы: «Мы учим Вас не запоминать, а понимать, что Вы читаете, способности думать и создавать новые идеи, знать, где найти тот материал, что Вам понадобится для исследований, цель должна быть во всем, что Вы делаете, каждый эксперимент должен отвечать на поставленный вопрос, интенсивная экспериментальная работа не означает хорошая работа, она должна проходить на основании анализа всех предыдущих работ, их обдумывания, планирования и множества других принципов научного подхода». Я выбрала кафедру катализа как специальность, поскольку в то время это была одна из двух наиболее «сильных» кафедр химического факультета. В 1981 году я защитила кандидатскую диссертацию на тему «Жидкофазное окисление С3-С4 олефинов на палладиевых катализаторах» в Институте органического катализа и электрохимии АН КазССР. Другой увлекательный период в моей научной карьере начался, когда я впервые увидела СВС эксперимент. Это было мощное горение большого образца состава Al + Cr2O3. Я сразу же решила попробовать этот метод как метод синтеза катализаторов. Работа была необыкновенно интересной. Мне довелось испытать ни с чем не сравнимое ощущение – быть свидетелем рождения нового направления в науке, в которой делаешь первые шаги. Мы отлично понимали необходимость расширения исследований, привлечения молодежи, поэтому мы ре-


С академиком А.Г. Мержановым на СВС-2009 в Армении шили заключить договора для получения значительного финансирования с Туполевским и Жуковским конструкторскими бюро на создание высокотемпературных огнеупоров для термозащиты космических аппаратов и межконтинентальных самолетов. Это стало вторым новым направлением СВС (самораспространяющимся высокотемпературным синтезом) развиваемым в нашей, благодаря этим договорам – созданной и хорошо оборудованной лаборатории, в которой в разное время работало от 10 до 20 человек. СВС результаты были настолько увлекательными, что мы не хотели уходить домой, работая допоздна. Это был один из наиболее интересных периодов моей жизни, когда царил фантастический климат создания нового, получения замечательных результатов каждый день. Одним из огромных удовольствий было наблюдать, как студенты вырастают в настоящих ученых, как учатся думать и создавать новые идеи. Эти направления были новыми в науке, поэтому были защищены кандидатские диссертации, и в 1991 году я также защитила докторскую диссертацию на тему «Самораспространяющийся высокотемпературный синтез катализаторов и носителей» в Институте структурной макрокинетики и проблем материаловедения АН СССР в Москве. В этом Институте, возглавляемом Мержановым А.Г., был открыт метод СВС. Многие годы ИСМАН финансировал наши исследования. В нашей лаборатории были развиты многие тех-

нологии, которые были применены для производства СВС материалов в промышленном масштабе. Одной из таких технологий стала СВС пигментов. Вначале эта 37

На церемонии награждения женщины года На выставке моих картин july - august №4


С моими студентами в Афинах технология возникла как побочный результат работы над созданием высокотемпературных материалов, но затем стала новым направлением в науке. Эта технология помогала нам выживать в трудный период 90-х, когда мы продавали пигменты различным организациям бывшего СССР (в основном керамические и пластмассовые заводы). Наука тогда не финансировалась государством, все хоз. договора были остановлены, в лаборатории остались немногие. 38

Что повлияло на Ваше решение продолжить свою научную карьеру в Греции? Какие трудности Вы испытали в адаптационный период? В 1993-1994гг я получала приглашение читать лекции в Афинском Политехническом университете.

В то время я приняла решение работать в Греции. Немаловажным фактором в принятии этого нелегкого решения было создание возможности хорошего будущего для моей дочки Татьяны (она смогла поступить в Афинах и позже закончила Нью-Йоркский университет в США, сейчас живет в Калифорнии). В Советское время все наши работы по СВС были закрытыми и мы не имели права публиковать их в зарубежных журналах (в это время у меня было уже 100 публикаций). В Греции я поняла, что никто не знает о наших работах, и я начала обобщать результаты, проводить дополнительные исследования и публиковать их. Понадобились года, чтобы эти исследования стали признанными. Другой проблемой было то, что в Советское время не было системы определения значимости журналов, поэтому за рубежом не было возможности доказать, насколько значительны результаты, опубликованные в таких журналах. Как следствие, нет объективной оценки работы специалиста за рубежом, это означает, что ученый за рубежом, если у него нет публикаций в международных журналах, должен практически начинать заново свое подтверждение статуса в научном мире. Кроме того, в большинстве стран (кроме Англии и Германии) нет ученой степени доктора наук и трудно объяснить, что это намного больше, чем кандидат наук, это означает, что доктор наук здесь считается кандидатом наук, в лучшем случае могут быть засчитаны две кандидатские степени. Процесс оценки

На фотографии слева: директор Space Portal - NASA Ames Research Center Dr. Daniel Rasky, президент JUSTSAP, президент IVA,Ltd, S.Day, зав.стратегического отдела NASA Jim Grady на встрече на Гавайях по лунной программе в 2009. На второй фотографии: разработчик программ NASA’s Apollo, Shuttle, ISS, президент JAMSS America, Inc.D. Bland и президент JUSTSAP-Japan, президент of PROSAP, Inc. Проф.О. Odawara во время встречи в Токио в 2010. №4 july - august


академических степеней очень медленный и сложный. Во многих случаях ученые из бывшего СССР должны дополнительно сдавать экзамены на языке страны, где они находятся для того, чтобы получить эквивалентный в данной стране диплом. Например, для подтверждения диплома химика надо сдать экзамен по биологии, который здесь преподается на химфаке. Это не просто. Поэтому многие специалисты из бывшего СССР не могут работать по специальности, кроме того, очень сложно найти работу в научных учреждениях. Другой трудностью является потеря всех пенсионных вкладов, поскольку нет договоренностей между странами, и поэтому приходится зарабатывать пенсию с нуля. Но все преодолимо, если есть цель, желание и если много работать, ведь выбрали же меня в Греции женщиной года за достижения в области науки. В сложные моменты помогает расслабиться хобби. Какие результаты, полученные в Греции, вы считаете наиболее важными? Работа в центре «Демокритос» дала мне множество возможностей. Я смогла продолжить мои научные исследования, писать статьи, обзоры, публиковать их в центральных международных журналах, иметь возможность работать со многими студентами, использовать новейшее оборудование, участвовать в многочисленных международных конференциях, а также, став известной в своей области, получать приглашения прочитать лекции от различных организаций мира: США, Канады, Японии, Франции, Италии, Кореи, Испании и т.д. Появилась возможность работы в Европейской комиссии и приглашения быть членом комитета по определению научных направлений в Греции, а также работать вместе в одной команде со многими ведущими учеными из различных стран. Очень важным достижением была работа с ESA (Европейское космическое агентство) по созданию теплозащиты для спутников, которое переросло в новый европейский проект с участием 10 организаций из 8 стран. Проводятся исследования и по лунной программе. В катализе работы велись по разработке катализаторов для процессов окисления, гидрирования, дегидрирования, окислительной дегидродимеризации, пиролиза и т.д., а также по промышленному применению катализаторов пиролиза нафты в Корее. Исследовался процесс цветообразования для СВС и других типов пигментов.

Интересные исследования проводились по горению в тонком слое и при комнатной температуре, исследования по применению СВС для охраны окружающей среды и для получения материалов для ТОКАМАК. Какой видится наука Казахстана извне? Что, повашему, нужно сделать для ее выживания и роста? Я считаю, что уровень науки в Казахстане высок. Я могу с уверенностью констатировать выдающиеся достижения казахстанской науки в области катализа и процессов горения, поскольку я постоянно слежу за этими исследованиями. Для развития науки нужны вложения. Одним из источников финансовой поддержки являются Европейские проекты. В течение многих лет я работаю экспертом Европейской комиссии по оценке проектов по программам GROWTH и FP6 (Marie Curie, STREP, NEST, SME, NOE), а также завершенных работ по проектам EVIMP, DRITE/EURAM, IMT, CRAFT, SMT и M&T, SME pact, IST, EESD-ENERGY, QOL, ITTE и т.д. На основании всего этого опыта могу сказать, что главной причиной отказа проектов с участием стран бывшего СССР является плохой английский (эксперты не понимают, что написано), отсутствие данных о значимости публикаций в этих странах, а значит и уровня специалистов, участвующих в проекте, а также отсутствие специалистов по написанию проектов. Практика показывает, что организации, где работают отделы по написанию таких проектов, получают наиболее часто финансирование. Очень важно ученым Казахстана переориентироваться на написание статей в международных журналах с высоким индексом цитирования. Международные конференции открывают двери к новым международным сотрудничествам, получению значительных грантов и являются кратчайшим путем к международному признанию исследований. Молодым ученым хочется пожелать верить в свои силы, не бояться ставить сложные, амбициозные цели, быть компетентными в своей области исследований, никогда не терять увлеченности заниматься наукой. В заключении мне хотелось бы сказать, что я считаю себя счастливым человеком, потому что я занимаюсь тем, что мне очень нравится. Я хочу выразить глубокую благодарность моим любимым родителям, прекрасным преподавателям и сотрудникам, с которыми я работала, а также выдающимся ученым нашего времени, которых я знаю. Все эти люди дали мне сил идти вперед. july - august №4

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Professor Galina Xanthopoulou (PhD, DSc) works at the National Center of scientific Research “Demokritos”, in Athens, Greece. She is the author of more than 250 publications and has 40 patents on catalysis, combustion processes in solid phase, ceramic materials and environment. She is a member of editorial boards of quite a few international journals and a Consultant to the European Commission.

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Can you tell us a few words about the center you work in? The National Centre of Scientific Research «DEMOKRITOS» was founded in 1958 as a decentralized public service and was initially named Nuclear Research Centre «DEMOKRITOS». The initial aim of the Centre was the utilization of the advantages of nuclear energy for peaceful aims. Within this framework and for the first time in the contemporary history of Greece, the repatriation of many Greek scientists emerged. These scientists gradually developed the structures and the organization of scientific research in Greece and participated in the configuration of the Centre as a really pioneering multi-branch centre. In 1985, the Centre was renamed as National Centre of Scientific Research «DEMOKRITOS» (N.C.S.R. «Demokritos») and became a self-administered governmental legal entity, under the supervision of the General Secretariat of Research and Technology (G.S.R.T.) of the Ministry of Development.

№4 july - august

Nowadays, the scientific activities of the largest in Greece Research Center (850 personnel, out of which 650 are scientists) take place in eight administratively independent Institutes: Institute of Nuclear Physics, Institute of Nuclear Technology and Radiation Protection, Institute of Materials Science, Institute of Telecommunications and Informatics, Institute of Microelectronics, Institute of Physical Chemistry, Institute of Biology and Institute of Radio-Pharmaceuticals. The activities of these Institutes concern sectors such as nuclear physics and astroparticles, energy-environment, nanotechnology, microsystems, integrated telecommunications and informatics technology systems, modern technologies for cultural heritage, control of environmental pollutants, nuclear technology and radiation protection, accelerative systems technologies and detector devices, generation and characterization of innovative materials, bioactive molecules, natural products and biotechnology, health and biotechnology. According to data for 2009 30 % of the total scientific performance of Greek Research Centers comes from “Demokritos”. “Demokritos” has 557 Publications in referee Journals for 2009 and more than 4000 during the last 10 years. Also, “Demokritos” has 437 publications from meetings in 2009 and more than 5000 in the last 10 years, with more than 35000 citations. Each year “Demokritos” organizes about 30 meetings and workshops and supervises about 20 PhD students, 20 master degree students and 35 diploma students. The Lefkipos Technology Park of NCSR “Demokritos” has created 22 spin-off companies in the last 5 years.


Each year “Demokritos” organizes summer school programmes with lectures of “Demokritos” scientists on the state of the art in various disciplines, attended by approximately 250 young university undergraduates and graduates. Why you take the decision to be a scientist? Can you tell us about your education and scientific carrier? The decision to be a chemist was taken very early, during childhood, when my mother Ivankova A. I., who was all her life successfully working in analytical chemistry, took me to her laboratory in the Institute of Mineral Row Materials. I was 5 years old then, but I still remember the magical world of colored solvents in glass bottles, complicated installations, scientists in white lab coats. My father, a chemist and academic (Ksandopulo G.I.), a well known scientist in combustion processes, was just beginning his carrier in the 60’s and I saw him work very hard at home. I would say that these memories of my parents, their excitement about the chemical science, the huge respect they enjoyed by fellow scientists, determined my decision to follow the same profession. A very important part in my decision was the opportunity I had to see and listen to famous and very talented scientists who were often guests at our house when attending conferences in Almaty, such as Nobel prize winner Semenov N.N., academics such as Zeldovich Ya. B., Emanuel N.M., Enikolopov N.S., Kondratyev V.N., Talroze V.L., Berlin A.A.(now academic and director of the Semenov Institute of Chemical Physics), professors Potehin G.S., Gershenzon U. M., Vedeneev V.L. and Merzhanov A.G. Their works are significant events in science. I admired these people and my farther said the very wise words: “If you want to be among such interesting people you have to study and work a lot, you have to grow your knowledge, as people like to communicate with equal personalities”. That was the key idea that reflected my future. I attended chemical School N39 with very good teachers and then enrolled to the Chemical Faculty of Kazakh State University named S.M.Kirov (now alFarabi), where at that time taught professors gifted in teaching such as Usanovich M.I.,Sokolskii D.V., Mirkin V.A., Solomin A.V., Zorov G.V., Streltsova V.M., Fasman A.B., Druz V. A. and many others. I remember them saying: “We are teaching you not to remember but to understand what you are reading, to be able to think and to create new ideas, also to know how and where to find what you are looking for”, “put aim in everything you are doing, every experiment must answer

some question”, “intensive experimental work does not mean good work, a lot of reading, analyzing of results, thinking, planning must be included” and many others such principles of scientific thought. I chose catalysis as specialty, because at that time it was one of the two most intensely developing groups of the chemical department. In 1983 I defended my PhD thesis “Liquid phase C3-C4 olefin’s oxidation on Pd catalysts” at the Institute of Catalysis and Electrochemistry in Almaty. Another exciting period in my scientific carrier started with the first SHS experiment I saw. It was a very powerful combustion of a big sample of Al+ Cr2O3. I decided then that I would definitely try to use this method for synthesis of catalysts. The work was extremely interesting! I was lucky to experience the incomparable feeling of birth of a new direction in science, in which one is taking the first steps. We realized that it was necessary to attract young scientists, to make wide scale studies, that’s why we made significant financial agreements with the Tupolev and Zhukovskii Construction companies for the development of high temperature refractories for spaceships and for intercontinental planes.It was the second new direction in SHS we were developing

My parents and daughter

july - august №4

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At the 40th Jubilee of SHS in ISMAN, Moscow(2007) with colleagues from France and Russia.

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and this work helped us establish a well equipped laboratory with a 10-20 scientists/technicians capacity. SHS results were exciting, we didn’t want to go home, working until late. It was one of the best periods in my life, a fantastic climate of doing together something new, exciting results every day. One of the great pleasures was to watch how quickly students grew into real scientists, how they started to create their own ideas. This work of our laboratory was considered as a new direction in science and quite a few PhD works were defended. In 1991 I defended my Doctor of Science thesis “Selfpropagating high temperature synthesis of catalysts and

carriers” at the Institute of Structural Microkinetics and Materials Science in Moscow. This institute (Director was A.G. Merzhanov), in which SHS processes were discovered, supported financially our research for many years. Our laboratory developed a lot of new technologies which were used for industrial scale production of SHS products. One of them was SHS pigments, another new direction in science. This research appear as side results when we study synthesis of spinels as refractories materials. As it happened, this work permitted us to survive the very difficult period of the 90s, by selling pigments to different organizations of former USSR. This period was characterized by significant decrease in interest to science, which was not supported by the state. The Laboratory became very small. What influenced you in taking the decision to work in Greece? What difficulties did you have during adaptation period ? In 1993-1994 I received an invitation to read lectures at the Athens Polytechnic University. At that time I took decision to work in Greece. Very important for this decision was that there I could prepare a good future for my daughter Tatyana (later she had the opportunity to study in Greece and then in the USA, New York University).

President of NCSR “Demokritos” prof..D. Niarhos and fellow scientists from Russia and Greece. №4 july - august


During the USSR period all our SHS work was considered secret by the state and we couldn’t publish abroad (at that time I had about 100 publications ! ). Nobody knew of our work abroad. In Greece I had to start to update results and publish them. It took years to be known. There was no citation index system in the USSR, which could show how important were the publications in the central, well known in the USSR journals, therefore no chance to show the significance of the work published in the USSR. That’s why there could be no objective evaluation of these publications abroad. This means that at that time scientists from the former USSR had to start from the beginning to establish their status in science internationally. The other problem was that in most countries (except England and Germany) there is no post-doctorate Doctor of Science degree and it was difficult to explain that it was much more than a PhD degree, there was no equivalent for it and that meant that my DSc was considered here just as a PhD. The process of evaluation of all academic titles was very complicated and slow. In many cases scientists from the former USSR had to pass additional exams to be evaluated as equivalent to Greek diplomas. For example, you had to pass exams, in Greek, in Biology if you want to receive conformation of your diploma from the Kazakh State University, as a Chemist. That’s why many scientists from the former USSR couldn’t get it and work on their specialty. Another reason for that is that it is very difficult to find work for scientists in Greece.

The other big problem was that all pension insurance contributions for years of work in the USSR and Kazakhstan - were not accepted (because there is no bilateral agreement between these countries and Greece) and was necessary to start pension insurance contributions from the beginning. But one can resolve all kinds of problems if one has an aim and the will to work hard. For me one of the sign, that adaptation period finalized was that I was selected for woman of the year in Greece for achievements in Science. In difficult moments a hobby helps! My hobby is painting. What are the main results of your work in Greece? Work in NCRS “Demokritos” brought me a lot of opportunities. It became possible to continue my work according to my scientific interests, to work on writing reviews, to publish in the main international scientific journals, to have many undergraduate and graduate students, to use modern equipment, to participate in a large number of international conferences. Also, to become known and to have opportunities to be invited to deliver lectures to different scientific organizations of the world in the USA, Canada, Japan, France, Italy, Korea, Spain etc. It also brought me the opportunity to work for the European Commission and to be invited to be a member of the Committee of Determination of Future Directions in Science in Greece and to work

At the ceremony of woman of the Year Award (Athens,Greece)

Exhibition of my paintings july - august №4

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At the Planetary Probe Workshop which we organized for NASA and ESA in 2005 Anavyssos, Greece,(on my left, prof..J.M..Muylaert Department Head of ESA).On the second photo: Meeting in Seoul, Korea, with prof. W.H.Lee, Head of Department in LG Chemical

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together in teams of well known scientists from different countries. One of the important results was the work with ESA (European Space Agency) on the development of heat protection for probes. Very important was work with ESA for hybrid thermal protection system for probes. Now we continue this work in the frame of new FP-7 project in which participate 10 organizations from 8 countries. We also work on moon program. In catalysis, the most important scientific work was the development of high active SHS catalysts for processes of oxidation, hydrogenation, dehydrogenation, oxidation dehydrodimerization, pyrolysis etc. and industrial applications of the naphtha pyrolisys catalyst in Korea. Process of color formation was studied for SHS and other types of pigments. Interesting results were received for combustion in thin layer and combustion at room temperature. Very important work was for environmental application of SHS and synthesis of materials for fusion reactor. How do you evaluate Kazakhstan science from abroad? What do you think must be done for its development? I believe that Kazakhstan science is at a very high level. I am sure about outstanding achievements in catalysis and combustion processes (works which I follow all the time). I think that for the development of science is necessary to have good investments. One of the sources of financial support is European Union projects. I have been working as Expert Evaluator for European Commission Proposals in the Programmes Growth and FP6 (Marie Curie, STREP, NEST, SME, NOE). Evaluations included technical, economic and socio-economic impact. I am currently working as Consultant to №4 july - august

the European Commission on the Project EVIMP, as evaluator of completed projects within the European Commission Programmes BRITE/EURAM, IMT, CRAFT, SMT and M&T. SMEpact, as evaluator of completed projects within the EC Programmes IST, EESD-ENERGY, GROWTH, STREP, QoL, ITTE etc. From all this experience I can say that the main reason of rejection of proposals from former USSR countries is bad English (experts don’t understand what is written), absence of data to qualify the importance of publications in the former USSR (citation index information), absence of specialists in all former USSR countries organizations who could be busy only in writing these projects (practice shows that organizations which have such specialists and even departments for preparing EC proposals get maximum financial support from projects), etc. It is very important to put emphasis on publications in international Journals with high citation index. International conferences are the door for starting new international collaborations, obtaining financial support and the shortest way to be come known in one’s direction of research. To young scientists I would like to give the advice to believe in their capabilities, not to be afraid to set for themselves high goals, to be highly competent in their region of research, never to lose the excitement of working in science. In conclusion, I want to say that I consider myself to be very lucky to do in my life what I really like. I want to express my deep gratitude to my parents and my excellent teachers, my professors of the universities I studied and my collaborators I was happy to work with, as well as to those outstanding scientists of our time whom I have met and who have given me the strength to go even further.


УДК 542.91:542.973

SELF-PROPAGATING HIGHTEMPERATURE SYNTHESIS AS METHOD OF CATALYSTS PRODUCTION G. Xanthopoulou Institute of Materials Science, National Centre for Scientific Research ”Demokritos”, Aghia Paraskevi Attikis, 15310, Greece. [email protected]

Самораспространяющийся высокотемпературный синтез (СВС) является новым методом получения нового класса катализаторов различного применения на основе металлов, сплавов, оксидов, шпинелей и т.д. СВС представляет собой режим протекания сильной экзотермической реакции (реакции горения), в котором тепловыделение локализовано в слое и передается от слоя к слою путем теплопередачи. В условиях быстрых скоростей реакций горения и охлаждения образуются структуры с высокой концентрацией дефектов промежуточных и нестехиометрических соединений, которые являются одной из причин высокой активности СВС катализаторов. Проведены исследования физико-химических и механических свойств широкого спектра синтезированных СВС катализаторов. В результате этих исследований учеными различных стран мира найдены СВС материалы, обладающие высокой каталитической активностью, перспективные для многих промышленных процессов. В этом обзоре описывается СВС метод, его преимущества, как метода приготовления высокоактивных катализаторов для процессов нейтрализации выхлопных газов, дегидродимеризации метана, пиролиза, гидрирования и др. Металлдар, құймалар, оксидтер, шпинельдер және т.б. әртүрлі қолданыс негізіндегі жаңа класты катализаторлар алудың жаңа әдісі жоғары температуралы өздігімен таралатын синтез деп аталады (ЖТӨТС). ЖТӨТС қатты экзотермиялық реакцияның өту режимі (жану реакциясы) онда жылу бөлінуі қабатта шоғырланып қабаттан қабатқа жылу берілуі арқылы жүреді. ЖТӨТС катализаторларының белсенділігінің бірден бір себебі тез жылдамдықтың негізінде жүретін жану және суыту реакцияларында дефекттердің жоғары концентрациясымен аралық және стехиометриясыз құрылымдар түзетін қосылыстардың түзілуімен байланысты болады. Кең көлемде синтезделіп алынған ЖТӨТС катализаторларының фиизко-химиялық және механикалық қасиеттерін зерттеу жүргізілді. Әлемнің әр түрлі елдеріндегі ғалымдардың зерттеулерінің нәтижесінде көптеген өндірістік процестердің болашағы бар жоғары каталитикалық белсенділігіне ие ЖТӨСТ материалдары табылды. Бұл шолуда ЖТӨСТ әдісі, әсіресе жоғары белсенді катализаторларын өндірістік газдарды, метанның дегидродимеризациясы, пиролиз, гидрлеу және т.б. процестерде бейтараптау үшін қолданылатын катализаторларды дайындаудың әдістері және оның қолайлы жақтары көрсетілген.

Abstract The Self-Propagating High-Temperature Synthesis (SHS) method is being developed for the production of

a new class of active catalyst materials based on metals, alloys, metal oxides and spinels for various applications. The conditions of quick velocities of combusjuly - august №4

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tion and cooling processes helps of catalytic active structures synthesis, due to formation of high concentration of defect structures of intermediate and nonstoichiometric compounds. A large range of materials have been produced and characterized by a variety of physico-chemical and mechanical tests. A number of catalytically active SHS materials all over the world have been identified which offer promise for applications in huge range of processes. This report reviews briefly the SHS method, its advantages and discusses a number of its applications such as highly active catalysts for exhaust emission control, methane conversion, dehydrodimerization, pyrolysis and many others processes. Keywords: Self-propagating high-temperature synthesis, SHS catalysts and carriers, catalytic properties, solution combustion synthesis.

1. Introduction SHS is relatively new method of the catalysts and carriers synthesis.

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The SHS method SHS method is being developed worldwide [1-2] for the low-cost production of engineering and functional materials such as advanced ceramics, intermetallics, catalysts and magnetic materials. The method exploits self-sustaining solid-flame combustion reactions for the internal development of very high temperatures over very short periods. It therefore offers many advantages over traditional methods such as much lower energy costs, ease of manufacture and capability for producing materials with unique properties and characteristics. SHS method was first invented in 1967 [1] in the ex Soviet Union but only became known worldwide in the beginning of the 80’s.Using SHS, composition, structure and properties of the materials can be regulated to satisfy the stringent requirements of many applications. SHS can start without initiation at preheating temperature when chemical reactions start. At room temperature initiation can be by electrically heated element. Once initiated, combustion is self-sustaining and proceeds by a combustion wave propagating through the compacted material from the initiation side to the opposite side and is completed in a time of a few seconds to a few minutes. The material in front of the propagating wave is preheated by the heat generated by the combustion and the material behind the combustion front is rapidly cooled. A schematic diagram of the SHS process is shown in Figure 1. №4 july - august

Figure1. Scheme of SHS process The basic principles of SHS can thus be summarized as follows [2,3]: Rapid auto wave combustion-like self-sustaining reactions yielding resultant products of desired composition and structure, complete or partial elimination of external energy supply by the utilization of the internal heat released in the chemical reactions, control of the process rate, temperature, degree of conversion and composition and structure of products by variation in the rates of heat release and transfer. In many cases SHS offers greater benefits in comparison with traditional methods especially as regards lower production costs and manufacturing advantages [2,4] but also in terms of microstructure and superior properties. In addition, the environmental impact of SHS is very much lower than that of the traditional method, a fact which decreases even further the indirect cost of production [2-3]. As a result, SHS has now become an extensively studied discipline and is often regarded as a link between combustion theory and materials science.

2. SHS catalysts technology and formation mechanism The first large scale and systematic research of SHS catalysts start in the 80s in Combustion problem Institute, Almaty, Kazakhstan. It was found, that method offers a good possibility for the preparation of new, active ceramic catalysts and carriers with compositions, structure and properties which satisfy the stringent requirements of many applications [3-5]. The interest to SHS catalysts is growing every year and now many countries intensively working with SHS and combustion synthesis catalysts: Russia, USA, Kazakhstan, Japan, Armenia, Greece, Brazil, Spain, Portugal, Armenia, Korea, India, China, Puerto Rico, Malaysia, etc. Such interest to SHS catalyst can be explained by high activity of catalysts prepared by this methods and advantages of SHS method in comparison with


traditional methods of preparation of catalysts. The main differences of SHS method in comparison with other methods of preparation of catalysts are: highly exothermic reaction of a mixture of powders, low preheating temperature but very high reaction (combustion) temperatures 1000 - 3000oC, very high heating and cooling rates: 103 - 106 oC/sec, very short completion times, of the order of minutes. Method is attractive for industrial production: much lower energy consumption than traditional production methods, much lower energy costs, possibility for “just-in-time” manufacturing, high productivity, cheap catalysts, relatively simple process - easily adaptable to industrial scale, controlled physico-chemical properties of the products, large range of new materials which can be used in catalysis, it has wide diapason of structural forms of products from granules of different size to blocks of honeycomb structure and different geometric forms. In the base of Self-Propagating High Temperature synthesis (SHS) of catalysts lays fundamental studies of structural microkinetics, study of strait and reversed bonds between chemical reactions velocities, heat and mass exchange in the structural conversions. Such technology permits realization of transformation from initial batch structure destruction to structure formation in the combustion products with catalytic active centers origination; at the same time it permits regulation of physico-chemical properties of synthesized materials. The sources for such technology are metals, oxides, salts ores, wastes. Extensive studies were over the last 30 years for the production of catalysts on the basis of the reactions (M is metal): M1 + M2O => M1O + M2 + MxAly + M1 M2O + Q M1 + M2=> M1M2 M + C => MC M +B=> MB M + N2 => MNx Various compositions and reaction conditions have yielded promising catalysts for many processes. Many of the new materials can only be produced by SHS. New active catalysts were found for: oxidation of CO, methane and hydrocarbons, dehydrogenation of hydrocarbons, hydrogenation of unsaturated hydrocarbons, oxidative dehydrodimerization of methane, pyrolysis of petrol, diesel, naphtha, other fuels; ammonia synthesis and other processes. In the [3-5] for the first time is developed general conception SHS catalysts production with high mechanical properties, were found and developed optimal conditions of SH synthesis, studied genesis of phase composition, structure-mechanical, catalytic

properties of SHS catalysts and carriers on the base of metals, oxides, spinels, intermetallic compounds of I-VIII groups of periodic system. It was found that prepared SHS materials are new class of catalysts and carriers, which is not possible to produce by traditional methods of chemical technology. Possibilities of new method were demonstrated. In [4-8] for the first time was studied mechanism of catalysts and carriers formation in the combustion wave (Figure 2), were discovered main stages of process (Table 1), including: preheating, melting and splitting of liquid phase, first structure formation with oxidizing-reducing reactions, secondary structure formation in the process of further reaction of components, final structure formation in the process of cooling (Table 1).

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Figure 2. Zones of the combustion wave The conditions under which many SHS ceramic catalysts are cooled after combustion were found to significantly influence their composition, structure, properties and catalytic activity (Table 2) [8]. During self-sustaining exothermic combustion of carefully designed and controlled mixtures of powders, the synthesis temperature can reach 1000-3000 oC over a very short total time of reaction: of the order of a few seconds. Under these conditions, the materials synthesized are characterized by a very high content of crystal lattice defects which is very significant as far as catalytic properties are concerned, as they act as active centers for catalysis. Following the passage of the combustion wave, the material behind the wave front starts cooling - the final structure and composition depends on the rate and nature of cooling. Figure 1 shows a concentration profile of the wave of combustion under SHS conditions for an iron containing system [8], (initial SHS charge contained powders of Al, Mg, Mg(NO3)2, FeSO4). Five zones of structural and chemical conversion can be distinguished whose characteristics are tabulated in Table 1. Zone V is the cooljuly - august №4


Table 1. Zones of conversion during SHS

Zone of structural conversion

I.

Preheat zone

II

Decomposition and melting zone

III

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Heat release zone (formation of primary structure)

CharacterApistic period proximate of zone conversion existence, period, (sec) (sec)

Structural conversion

Chemical conversion

Depends Depends Τ0 - Τmelt on preheat on preheat (Τdecomposition) period of period of specimen specimen

No conversion

Dehydration

10-2 - 10-3

Diffussion of Al with simultaneous chemical reaction

Decomposition reactions (partial)

2

10-2

Formation of small (1 μm) grains of spinels and oxides

Oxidationreduction reaction

Depends on cooling rate of material


Grain growth of spinels and oxides (up to approx 10 μm)



Grain growth of spinels and oxides (up to approx 10 μm)

Temperature range

Τmelt, Τdecomposition

Τmelt Τcombustion

Burn-down zone (formation Τcomb - Τmelt of secondary IV (Τdecomposition) structure, recrystallization)

V

Cooling zone (formation of secondary structure)

Τmelt, Τdecomposition

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ing zone and it is obvious that the composition of the materials is still changing. By cooling the specimen under various rates and conditions (from a few hundreds to hundreds of thousands of degrees per minute), it is

Reaction product

Oxidation (burning down)

Completion of reaction

(Cooling)

No chemical interaction

thus possible to obtain a range of compositions and also change the lattice defect concentration. It was found, [3-8] that the main parameters of SH synthesis process of catalysts and carriers is maxi-

Figure 3. The processing conditions that influence the final physico-chemical properties of SHS catalysts №4 july - august


mum temperature in the synthesis wave, which depends from batch composition, dispersity of reducer and oxidizer (less but also from dispersity of other components) and preheating temperature, that the most important from technological parameters of SHS catalysts and carriers are chemical composition and initial batch components dispersity, conditions of granulation and mixing of components, chemical composition of additives, conditions of shaping, conditions of preheating, initiation of SHS process, regime of cooling (Figure 3). It was found [4] that main parameters of regulated porosity formation in the SHS regime are maximum synthesis temperature and presence in the initial batch organic and inorganic substances easy gasified and burning out. SHS technology permits regulation of final catalyst porosity from 20 to 98% with required mechanical properties. One of the most important parameters is cooling conditions. The material based on the Al-Co-O was subjected to SHS combustion under identical conditions and then cooled at different conditions: in the furnace, in air (at room temperature), in brine (salt and water solution) and in liquid nitrogen (Table 2). The cooling rate mostly affects catalysts, because changing of composition and structure lead to changing of activity. At faster rates of cooling, more structural defects of the crystal lattice are generated (defects are the active centers of catalysts), increasing the material’s activity. But the final activity of the catalyst depends on both parameters: defect structure and composition. For example in the case of dehydrogenation, most important is the quantity of cobalt in the catalyst. In the case of the Al-Co-O system, the most active catalyst was found to be the one containing 28% Co (cooling in brine), the yield of hydrogen in this case being 90% (Table 2).

For the first time [3-5] were studied influences of different factors on the SHS catalysts surface area. It can be regulated from 5 to 20 m2/g during synthesis. Main reason of such low surface area is high temperatures during combustion; pore size is 500-10000Å (Figure 4). Further increasing of surface area up to 100-200m2/g can be only by additional treatment: impregnation, leaching, formation of honeycomb structure.

49

Figure 4. Radial pore distribution for SHS catalysts and carriers

Table 2. Influence of cooling conditions of cobalt base catalysts on their composition, physical properties and activity during pyrolysis of petrol (petrol flow 1ml/min, conversion 100%) Cooling conditions in brine in liquid N2 in air in furnace

Composition of the catalyst, wt%

Composition of gas products of pyrolysis, wt%

Physical Properties

CoAl2O4

CoO

Co

H2

CH4

C2H6

28

44

28

90

10

-

Compressive strength, MPa -

25

60

15

80

20

-

24.5

72.5

3

75

25

28

71

1

50

45

Density g/cm3

Specific surface area m2/g

-

-

-

45

21

6.6

0.7

-

15

60

2.5

1.1

5

12

77

2.3

1.4

Porosity %

july - august №4


50

It was offered [3-5] in principle new, very effective method of SHS catalysts and carriers synthesis. Developed scientific base of technology could be used for developing technology for industrial catalysts and carrier’s production. • Controlled physico-chemical properties of the products • Large range of new materials which can be used in catalysis • Very active catalysts for many industrial processes

nated, for example, into thin, pure cellulose paper and dried at room temperature. Further, such paper is locally ignited at room temperature and steady-state combustion front propagates along the reactive media. The maximum reaction temperature can be as high as 1000 oC, but reaction time owing to the rapid quenching of thin reacted layer, is less than 0.1 s. By this method also can be produced catalysts with surface area. Note, that amount of residual carbon in asprepared materials by IALC approach does not exceed 0.1 wt.%.

3. Solution combustion (SC) synthesis One of the new directions following SHS method is Solution combustion (SC) synthesis [9], which is also very prospective for synthesis of catalysts, because it permits to produce catalysts with high surface area. Solution combustion (SC) synthesis, takes place in an aqueous solution of the oxidizers (e.g. metals nitrites) and fuels (e.g. glycine, citric acid and urea). In conventional scheme, at certain temperature (100– 200oC) the reaction self-ignites through the entire reactive media (so-called volume combustion synthesis (VCS) mode) leading to the formation of fine solid products with tailored composition. Under equilibrium conditions, in general such combustion reactions can be represented as follows: modifications of the solution Mex(NO3)y + CH2NH2CO2H9 +O2 => MeO + CO2 +H2O + N2. Recently by prof. Mukasyan with collaborators from USA were developed modifications of the solution combustion synthesis. These methods include [10]. 1. Self-propagating sol–gel combustion (SSGC): the desired amount of metals nitrates + fuel solution is dried at room temperature to make a sol–gel like heterogeneous media, which was than locally ignited with the help of heated tungsten wire. As a result a self-sustained reaction wave steadily propagates along the media forming nano-powder of desired composition. This steady-state propagating mode allows more precise control of the material composition and structure as compared to conventional VCS scheme, which proceeds by thermal explosion. 2. Impregnated support combustion (ISC) method involves impregnation of reaction solution inside the porous structure of the inert solid support, followed by reaction initiation similar to those in SSGC mode. ISC permits synthesize of supported catalyst with extremely high surface areas (up to 200m2 g−1). 3. Impregnated active layers combustion (IALC) method. In this case, the reaction solution is impreg-

4. Reactive milling followed by SHS Another direction of SHS synthesis of catalysts is synthesis by reactive milling. Synthesis of WC catalysts by reactive milling, followed by Self-sustaining reaction for hydrogenation, methanation and ammonium synthesis was presented in work of prof. K.S. Martirosyan with collaborators from USA [11]. Also scientists from Brasil study reactive milling – SHS process for synthesis of catalysts on the base of WC, in the initial batch they take WO3, Mg, C [12]. Mechanical activation of Self-Propagating HighTemperature-Synthesized LaFeO3 to be used as catalyst for diesel soot oxidation was studied by prof. T. Akiyama with collaborators from Japan [13]. SHS catalysts and catalysts prepared by solution combustion synthesis were studied in number of different processes.

№4 july - august

5.Catalytic activity of SHS products 5.1.CO oxidation on SHS catalysts Oxide catalysts prepared using the self-propagating high-temperature synthesis (SHS) method were found to display high activity for oxidation of CO. Catalytic oxidation of carbon monoxide and propane on SHS sialon impregnated by oxides was studied in ISMAN (Russia) [14]. SHS-produced β-sialons Si6−z Alz Oz N8−z (z = 1, 3, 4) were tested as supports for oxidation catalysts comprising of unary, binary or ternary mixtures of transition metal (Cr, Mn, Fe, Co, Ni, Cu) oxides and also KMnO4 and K2Cr2O7.Oxides of transition metals(Cr, Mn, Fe, Co, Ni, Cu) were deposited onto sialon granules by cold impregnation.. In oxidation of CO and propane (C3H8), the highest activity was exhibited by the catalysts based on cobalt oxides (Figure 5): 100% conversion at 180oC. The performance of the best Co-containing catalysts immobilized on the β-sialon with z = 1 was found to be close to that


of the commercially available Pt-containing catalyst. Due to their high heat resistance and thermal stability, β-sialons can withstand high temperatures and operate in strongly abrasive and acidic media, and thus challenge such widely used catalyst carriers as alumina and aluminosilicates.

Figure 5. Temperature dependence of catalyst activity in oxidation of CO and propane for (1) the 0.1–0.2-mm sialon (z = 3) granules bearing 6.8 wt % Co3O4 activated in a Fe(NO3)3 solution and (2) the 0.1–0.2-mm beads of commercially available catalyst carrier ShPK1; α = 1.5,GHSV = 120000 h–1 Comparison between SHS catalysts of the system Cu-Cr-O and commercial catalyst systems for carbon monoxide oxidation in exhaust gases of internal combustion engines were studied in Greece [15]. The results show that CuCr2O4 catalyst prepared by SHS used as crushed materials without carrier or additional treatment display equivalent activity to that displayed by conventional 0.5%Pd/Al2O3 system even though its specific area was only about 1m2/g as compared to about 90% for traditional Pd/Al2O3 catalysts with much higher specific area. Similar catalyst: Cu1-xNixCr2O4 produced by combustion synthesis for CO oxidation by Scientists from Brazil [16]. The surface self-propagating thermal synthesis (SSTS) of supported oxide catalysts was used by Russian group to produce supported oxide catalysts for deep oxidation of CO and methane [17]. Pd–CeO2 catalysts on a monolith support with a honeycomb structure have been prepared by surface self-propagating thermal synthesis (SSTS) [18]. The Pd–CeO2/Al2O3 monoliths prepared by SSTS are more active in CO oxidation, total hydrocarbon oxidation, and nitrogen oxide reduction than the catalysts obtained

by conventional impregnation. This is explained by the fact that the SSTS products have a larger specific surface area and their active component has a smaller particle size. 5.2. Low-temperature water gas shift reaction Ce1-xPtxO2-δ catalyst synthesized by reaction: (NH4)2Ce(NO3)6+H2PtCl6+C2H6N4O2=>Pt/CeO2 and show high catalytic activity in low-temperature water gas shift reaction. CO conversion (CO+H2O => H2+CO2) is found to be maximum at 200oC over Ce1-x PtxO2-δ catalysts without any methanation [19]. 5.3. Methane oxidation The self-propagating high-temperature synthesis method has been used to produce a range of oxide catalysts which have been found to be active for deep oxidation of methane /20/. The SHS materials studied include various compositions based on the systems K-Mn-Al-O, Al–Mn–Mg–O, Mg–Cr–O, Mg–Al–O, Mg– Cr–Al–O and Cu–Cr–O with and without the addition of Cerium oxide and an epoxide additive. Specific compositions of these systems were identified as being significantly active for this process (maximum conversion of up to 76%) and were thus investigated further. Many of the systems can be easily formed by extrusion and SHS into catalytically active, mechanically strong, honeycomb block structures in one step. Coating these active blocks with a known catalyst (known to be active in this process), was found to enhance the overall catalytic activity giving maximum conversion of up to 100% and offers an inexpensive and viable alternative to traditional catalyst systems. Supported Pd catalyst for high-temperature methane combustion was studied /21/ by examining the combustion synthesis preparation method. The major drawback of the SHS is that it leads to low surface area materials. The addition of low contents of lanthanides, especially cerium, showed to be effective to enhance the oxides texture. It was also seen that low loading of CeO2 well dispersed on alumina works as catalyst promoter on methane combustion. The same authors from Brazil [22] evaluated combustion synthesis as a preparation method of perovskites with cerium for methane oxidation. It was reported, that all perovskites catalysts which they study showed to be active in methane combustion. The results indicated that over the perovskites loaded with cerium the oxygen adsorbed onto the catalyst surface plays significant role in the activity of the catalysts. july - august №4

51


5.4. Methane oxidative dehydrodimerization Catalytic properties SHS borides and complex oxides were studied in methane oxidative dehydrodimerization, the yield of ethene is 7.2-16.8% [23-24]. Very active manganese, samarium and lead spinels based SHS catalysts (Figure 6) were found for oxidative dehydrodimerization of methane in other work [25-26], the maximum yield of ethene is 26%.

Figure 6. Oxidative dehydrodimerization of methane. Optimised Ethene yield on SHS catalysts 52

5.5.Carbon oxidation The first work on SHS catalysts soot oxidation published in 1995 [26]. Activity of various SHS powder and block catalysts was studied in process of burning out soot for the purifying of outgoing gases of diesel motor. Best results show Cu-Al-Mg-O SHS catalysts (soot burning out temperature is 420oC). Scientists from USA [27] study temperature programmed combustion of the catalytic carbon combustion over SHS CeCrO3 and La0.8Cr0.9Li0.1O3 catalysts micro- and nanostructured complex oxides powder. Carbon burned out temperature was 400oC for CeCrO3 and 500oC for La0.8Cr0.9Li0.1O3. Authors from Hokkaido University, Japan [28-29] study Self-Propagating High-Temperature Synthesis with post-heat treatment of La1−xSrxFeO3 (x = 0–1) perovskite as catalyst for soot combustion. La1−xSrxFeO3 perovskite, Sr-substituted LaFeO3, was prepared by Self-Propagating High-Temperature Synthesis and its catalytic activity for soot combustion was experimentally examined in comparison with that of a conventional Pt/Al2O3 catalyst. The soot combustion temperature of this product is as much as 1000 C lower than that of non-catalytic soot combustion. In other words, it had the same activity as that at only 200 C higher, in comparison to conventional Pt/Al2O3 catalyst. More significantly, average apparent activation energy of sample №4 july - august

with x = 0.8 calculated by Friedman method using TG/ DTA was approximately 15 kJ/mol lower than that of Pt/ Al2O3 catalyst. This result suggested that La1−xSrxFeO3 has the possibility to be an alternative catalyst to Pt/ Al2O3 catalyst. The group of prof. Akiyama studied also mechanical activation of self-propagating high-temperature synthesized LaFeO3 to be used as catalyst for diesel soot oxidation [30]. Proposed active catalyst of SHS LaFeO3 (LFO) as alternatives to precious metals such as platinum for promoting the oxidation of diesel particulate matter. Significantly, the LFO samples exhibited better catalytic activity for the oxidation of carbon black, though their surface area was smaller than that of Pt/Al2O3 (on LFO oxidation of the soot at 400oC, on Pt/Al2O3 485oC). 5.6. Oxidation of hydrocarbons, aldehides and methanol conversion In 1978 Russian scientists [31] show that titanium, niobium, molybdenum borides obtained by SHS method are active in the process of joint oxidation of nonene-1 and benzaldehyde. In 1981 they [32] show that molybdenum, cobalt borides obtained by SHS method were also very active (at temperatures 135150oC) in the process of oxidation of isobutene. Oxidation of styrene oxide and benzaldehyde were studied in 1984 [33] on SHS TiC catalysts. It was found, that transitional metal carbides are catalytically active in oxidation and reduction processes, in photo-and electrocatalysis WC, W2C, Mo2C, TiC, TaC widely used catalysts. In 2002 ceramics based on SmCoO3-δ prepared by combustion synthesis as a catalyst in hydrocarbons partial oxidation was studied [34]. The catalyst was prepared by reaction: Sm(NO3)3. 6H2O, Co(NO3)3 6H2O, Sr(NO3)3 6H2O, Pt (II) acetyl acetonate and urea (CO(NH2)2 as fuel => Sm0.95CoO3-δ, (Sm0.95Co3-δ)0.4Pt, Sm0.7Sr0.3CoO3-δ. The undoped sample (Sm0.95CoO3-δ) exhibits a methanol conversion of about 45%. The Pt impregnated samples, which have a ratio of Pt/Sm surface = 2, exhibit the best catalytic activity, methanol conversion is 63%. 5.7 Hydrogen oxidation Hydrogen oxidation on titanium carbides prepared by SHS was studied by Armenian scientists [35] It is shown that catalytic activity of Ti carbides grows with increase in carbon deficiency in a carbide sublattice in a TiC0.6 > TiC0.8 > TiC row. Spanish scientists [36] found active Pt–Ru–Ni anode electrocatalyst prepared by combustion synthesis


(employing two different fuels), that is, urea and sucrose for proton exchange membrane fuel cell (PEMFC).The results obtained reveal combustion synthesis as an appropriate method for preparing PEMFC electrocatalysts, due to its versatility, simplicity and fastness.

[40]. The efficiency of the skeleton nickel catalysts, prepared by leaching SHS aluminides, has been found to be well above for olefins hydrogenation than that of common NiR catalysts.

5.8 Pyrolysis of diesel fuel Catalytic pyrolysis of diesel fuel on SHS catalysts made of cobalt-doped Mg-Al-O spinels offer high yield of ethylene while coke yield is drastically reduced, in comparison with other catalytic systems and thermal pyrolysis (Figure 7) [37]. Catalytic pyrolysis of naphtha on SHS catalysts on complex oxide catalysts also is successful: the yield of ethane and propene is 51%.

Figure 8. Kinetic curves of potassium maleate, phenylacetylene, butindiol-1,4 hydrogenation on Ni-Reney and SHS catalysts 53

Figure 7. Concentration of Co3O4 in initial charge, mass % 5.9 Steam reforming of JP-8 surrogate, auto-reforming of sulfur containing fuels Solution combustion catalysts LaFe0.6Ni0.4O3/Al2O3 is characterized by high stability and activity for steam reforming of JP-8 surrogate (kerosene–based jet propulsion fuel) [38]. Full conversion was maintained during the duration of experiments (12 h) and hydrogen concentration is close to predicted theoretical limit (42%). Perovskite catalysts for the auto-reforming of sulfur containing fuels prepared by Solution combustion show good results [39]. 5.10. Hydrogenation Nickel-skeleton SHS catalysts and Ni-based catalysts show very high activity in process of hydrogenation of compounds with double and triple unsaturated bonds. For example Ni-SHS skeleton catalysts in potassium maleate hydrogenation at 40oC have 20% higher velocity of hydrogenation than industrial Ni-Raney catalyst [3-4] (Figure 8). Skeleton SHS catalysts were studied also in process of hexene-1 hydrogenation

5.11.Ammonia synthesis I It was found that for ammonia synthesis [41] activity of SHS catalysts are compatible with that of an industrial catalyst. 5.12. Generation hydrogen from water SHS catalysts (NixZn1-x)Fe2O4 and (MnxZn1-x)Fe2O4 (monolithic reactors ) were active in solar water splitting for hydrogen production [42]. The synthesized SHS catalyst systems are able to split water and generate hydrogen as the only product, at temperatures as low as 800oC with conversions reaching 80% in terms of water. 5.13 Production of hydrogen by the oxidative reforming of methanol Multi-component catalysts containing copper, zinc, zirconium, and palladium were prepared by a combustion synthesis method referred as impregnated layer combustion synthesis (ILCS) [43]. These catalysts were active and selective for the production of hydrogen by the oxidative reforming of methanol. ILCS involves impregnation of a reactive solution containing nitrated of the catalytic components and glycine which is impregnated into a cellulose substrate. The exothermic combustion of the mixture to form oxides led to the july - august №4


formation of a self-propagating combustion. It is shown that synthesis procedures and the presence of a ZrO2 support have a significant effect on Pd dispersion and on the resulting catalytic activity and selectivity. Catalyst with 3%Pd loaded in a second wave impregnation (SWI) method showed exceptional high activity for methanol conversion at low temperatures, whereas the ZrO2 supported catalyst displayed superior selectivity toward hydrogen production over the whole range of the temperatures investigated.

54

6. Conclusions Technology of catalysts production (metals/oxides, oxides, borides, carbides, nitrides, oxinitrides, alloys, etc.) and carriers by SHS and combustion synthesis is an advanced stage. There is possibility for “just in time” manufacturing of the SHS catalysts, which has low production costs and good competitiveness. The catalytic activity of many of the SHS materials is substantially better in comparison with non-SHS catalyst systems. Highly active SHS catalysts and carriers have been developed for a number of processes: • CO, NO, H2, hydrocarbons(CH4, nonene, isobutane, styrene, etc), aldehides, alcohols oxidation, • oxidative conversion of methane to synthesis gas, • dehydrodimerization of methane, • pyrolysis of diesel fuel, petrol, naphtha, • dehydrogenation, steam reforming of kerosene, • carbon combustion, • hydrogenation, • hydrodenitrogeneration and hydrodesulphurization reactions, • solar water splitting for hydrogen production, • production of hydrogen by the oxidative reforming of methanol, • ammonia synthesis, etc. New SHS catalysts for internal combustion engines offer higher activities for CO oxidation than commercial systems using Pd or Pt on Al2O3 or cordierite carriers, even at very low specific areas (about 1m2/g), often as low as 1% of those of noble-metal systems. Some of the new catalysts have potential for replacement of noble metal or other industrial catalysts. For example, catalysts Cu1-xNixCr2O4, Cu-Cr-O, Co-Cr-Al-O active at 160oC, supported oxide (Co3O4, CuO, Mn3O4) and spinel (CoMnOx, CuCoyOx) catalysts on SHS carriers β-sialons Si6–zAlzOzN8–z (z = 1, 3, 4) etc. Very active SHS catalysts were found for methane oxidation (K-Mn-Al-O, perovskites), oxidative conversion of methane (SHS spinel catalysts Fe-Al-O, Ni-Al-O, Ni-Fe-Al-O, Sn-Al-Mg-O, Co-Al-O), joint oxidation of non№4 july - august

ene-1, benzaldehyde and isobutene (TiB2, NbB2, CoB, MoB, MoB2, MoS2), oxidation and reduction processes, in photo and electrocatalysis (carbides WC, W2C, Mo2C, TiC, TaC), hydrocarbon partial oxidation (SmCoO3-δ prepared by combustion synthesis), dehydrodimerization of methane (LaCaB6-MgO, LaxMeCuzOy, Pb-Mg-O, K-Mn-O, Sm-Al-O, complex oxides YBa-Cu-O), pyrolysis of diesel fuel, petrol, naphtha (CoAl2O4, MgAl2O4,CoAl2O4), steam reforming of JP-8 surrogate (LaFeO3-based perovskite (La0.6Ce0.4Fe0.8− ZNi0.2O3−δ)), combustion of soot (Cu-Al-Mg-O, LaFeO3, La1−xSrxFeO3, CeCrO3, La0.8Cr0.9Li0.1O3), hydrogenation (NiAl2O4, NixAly skeleton catalysts), ammonia synthesis (FexAly ), etc. Carriers prepared by SHS method are already produced industrially. New SHS catalysts for pyrolysis of hydrocarbons offer high industrial potential as their high activity is accompanied by reduced coke production. SHS catalysts have industrial application, they are used for pyrolysis of naphtha. Very active catalysts were found for CH4, hydrocarbons oxidation, for dehydrodimerization of methane and others. The high catalytic activity at such low specific areas is related to both the SHS materials’ unique composition as well as their very high atomic defect concentration resulting from the SHS process conditions. Solution combustion synthesis is very prospective because of possibility of organizing high surface area. SHS and solution combustion synthesis can be considered as very successful method of synthesis of new cheap and very active catalysts and catalysts on carriers.

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Symposium on Self-Propagation High-temperature Synthesis, Moscow, 1991. P.110. 7. Gladoun (Xanthopoulou) G., Sergienko V. and Ksandopulo G.I., Int. J. of Self-Propagating High-Temperature Synthesis, 1997. V. 6. P.399. 8. Xanthopoulou G. and Vekinis G., International Journal of Self-Propagating High Temperature Synthesis, 1999. V.8. P.287. 9. Dinka P., Mukasyan A.S., Journal of Power Sources, 2007. V.167. P. 472. 10. Mukasyan A. S. and Dinka P., International Journal of Self-Propagating High-Temperature Synthesis, 2007. V.16. P. 23. 11. Martirosyan K.S., Litvinov D. and Luss D., Combustion of Heterogeneous Systems: Fundamentals and Applications for Materials Synthesis, 2007. P.67-101. 12. Passadora F.R., Maestrellia S.C., Palloneb R.F., Tomasia R., Materials Science Forum, 2005. V.498-499, P.648. 13. Taniguchi K., Hirano T., Tosho T., Akiyama T.,Catal Lett, 2009. V.130. P.362. 14. Borshch V.N., Zhuk S.Ya., Vakin N.A., Smirnov K.L., Borovinskaya I.P.and Merzhanov A.G., International Journal of Self-Propagating High-Temperature Synthesis, 2009. V.18, P.38. 15. Xanthopoulou G. and Vekinis G.: Applied Catalysis B: Environmental, 1998. V.19, P.37. 16. Pimentel P.M., Ginani M.F., Martinelli A. E., Melo D.M., Pedrosa A.M., Melo M.A., Material Science Forum, 2005. V.498-499. P.663. 17. Zav’yalova U.F., Tret’yakov V.F., Burdeinaya T.N., Lunin V.V., Shitova N.B., Ryzhova N.D., Shmakov A.N., Nizovskii A.I., and Tsyrul’nikov P.G., Kinetics and Catalysis, 2005. V.46. P.752. 18. Zav’yalova U.F., Barbashova P.S., Lermontov A.S., Shitova N.B., Tret’yakov V.F., Burdeinaya T.N., Lunin V.V., Drozdov V.A., Yashnik S.A., Ismagilov Z.R., Tsyrul’nikov P.G., Kinetics and Catalysis, 2007. V.48. P.162. 19. Beraa P., Malwadkarb S., Gayena A., Satyanarayanab C.V., Raob B.S., and Hegdea M.S., Catalysis Letters, 2004. V.96. P.3. 20. Xanthopoulou G. and Vekinis G, Applied Catalysis A: General, 2000. V.199. P.227. 21. Fraga M.A., Greca M.C. and Appel L.G., Utilization of Greenhouse Gases, 2003. V.852. P.375. 22. Fraga M.A., Pereira R.A. and Greca M.C., Materials Science Forum, 2006. V.530-531. P.696. 23. Merzhanov A.G.,et al., RU Patent, No.2000137, No.1806125,1991, Merzhanov A.G., et al., SU Patent, No.1685904, No. 1766498,1991.

24. Gladun G.G., Orinbekova Zh.G., Ksandopulo G.G., Grigoryan E.H., Merzhanov A.G., Borovinskaya I.P. and Nersesyan M.D., USSR Patent No.1729028, 1991. 25. Xanthopoulou G., Applied Catalysis A: General, Letters, 1999. V.185. P.185. 26. Xanthopoulou G., Chemical Engineering and Technology, 2001. V.24. P.1025. 27. Rodivilov S., Gostev S. and Gladoun G. (Xanthopoulou), Proc. of International Seminar Block Supports and Catalysts of Honey-Comb Structure, SanktPetersburg, Russia, 1995. P.65. 28. Martirosyan K.S., Litvinov D. and Luss D., Combustion of Heterogeneous Systems: Fundamentals and Application for Materials Synthesis, 2007. P.67. 29. Hirano T., Tosho T., Watanabe T. and Akiyama T., Journal of Alloys and Compounds, 2009. V.470. P.245. 30. Taniguchi K., Hirano T., Tosho T., Akiyama T., Catal Lett., 2009. V.130. P.362. 31. Tavadyan L.A., Maslov S.A.and Blumberg E.A., Neftekhimia, 1978. V.18. P.667. 32. Khirnova G.N., Bulygin M.G. and Blumberg E.A., Neftekhimia,1981. V.21, P.250. 33. Blumberg E.A. and Novikov Yu.D., Review of Sci. and Tech, Kinetica i Kataliz, 1984. V.25. P.269. 34. Chinarro E., Jurado J., Key Engineering Materials, 2002. V.206-213. P.1227. 35. Oganesyan T.K., Gukasyan G.S. and Nalbandyan A.B., Armenian Chim Zh., 1988. V.41. P.50. 36. Moreno B., Chinarro E., Pérez J.C. and Jurado J.R., Applied Catalysis B: Environmental, 2007. V.76. P.368. 37. Xanthopoulou G., Applied Catalysis A: General, 1999. V.182. P.285. 38. Dinka P. and Mukasyan A., J. Phys. Chem.B, 2005. V.109. P.21627. 39. Dinka P., Mukasyan A.S., Journal of Power Sources, 2007. V.167. P.472. 40. Lunin V.V., Grigoryan E.H., Kuznetsova N.N., Mikhal`chinets T.I., Symonyan A.V., Yukhvid V.I., Proceedings of SHS99 Symposium, Moscow, 1999; Merzhanov A.G., et al., RU Pat. No. 2050192, 1995. 41. Grigoryan E.N., International Journal of SelfPropagating High-Temperature Synthesis, 1997. V.6. P.307. 42. Agrafiotis C., Roeb M., Konstandopoulos A.G., Nalbandian L., Zaspalis V.T., Sattler C., Stobbe P., Steele A.M., Solar Energy, 2005. V.79. P.409. 43. Kumar A., Mukasyan A.S. and Wolf E.E., Applied Catalysis A: General, 2010. V.372. P.175. july - august №4

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УДК 547.211

КАТАЛИТИКАЛЫҚ ӨҢДЕУ АРҚЫЛЫ ТАБИҒИ ГАЗДАН СИНТЕЗ-ГАЗ АЛУ Т.С. Байжуманова Д.В. Сокольский атындағы органикалық катализ және электрохимия институты

Представлены результаты исследования процессов селективного каталитического окисления и парокислородной конверсии метана на нанесенных низкопроцентных катализаторах на основе благородных металлов на керамических блочных сотовых носителях. Определено влияние состава нанесенных блочных катализаторов и оптимальных концентраций катализаторов на блоке на эффективность в реакциях окисления СН4 в синтез-газ. Показано, что при суммарном содержании благородных металлов в составе катализатора 0,2–1,0 вес.% и атомном соотношении Pt:Ru ~ 1:1 наблюдаются 100% степени превращения исходного СН4 с селективностью по Н2 и СО 100%. 56

Results of research of catalytic oxidation and steam-oxygen conversion of methane on supported low-percentage catalysts on the basis of precious metals on ceramic block cellular carriers are presented. Influence of composition of supported block catalysts and optimum concentration of catalysts over the block on efficiency in reactions of oxidation of СН4 into synthesis-gas was determined. It was shown that 100% degree of transformation of initial СН4 with maximum selectivity by Н2 and CO are observed at 0,2-1,0 weight. % of total maintenance of precious metals and of Pt:Ru ~ 1:1 nuclear ratio.

Андатпа Мақалада метанның талғамды каталитикалық тотығу және буоттекті конверсия процестері үшін төмен пайызды асыл металдар негізіндегі катализаторларды керамикалық блокты ұялы тасымалдағыштарда зерттеу нәтижелері көрсетілді. Отырғызылған блокты катализаторлар құрамының және СН4-ның синтезгазға талғамды каталитикалық тотығу реакциясына блоктағы катализаторлардың тиімді концентрациясының жағдайлары анықталды. Катализатор құрамында асыл металлдар қоспасы сал.% 0,2–1,0 және атомдық қатынасы Pt:Ru ~ 1:1 болғанда, талғамдылығы Н2 және СО бойынша 100% және бастапқы СН4 тотығу дәрежесі 100% болытыны анықталды. №4 july - august

Түйінді сөздер: метан, синтез-газ, талғамды каталитикалық тотығу, блокты ұялы тасымалдағыштар.

1. Кіріспе Қазақстан табиғи газ қорлары бойынша әлемде 15-ші, ТМД-да 4-ші орынға ие, сондықтан алкандардың тотығу конверсия процестеріне арналған аса тиімді, талғамды және тұрақты катализаторларды жасау практикалық жағынан маңызды және стратегиялық міндеттерге ие мәселе болып табылады. Метан табиғи газдың негізгі компоненті және ол атмосфераға өткен жағдайда булы эффекттінің дамуына жағдай жасайтын газдардың негізгісі екені белгілі. Метанның атмосфераға тасталынуын қысқарту


едәуір оң экономикалық және экологиялық нәтижелерге алып келуге қабілетті. Бұндай байлықтың орынсыз қолданылуы және өнеркәсіптік өңдеу әдістерінің жоқтығына байланысты, метанды синтездеу процестерінде қолданатын катализаторларды өңдеуде тереңдетілген зерттеулер дамуы теориялық және практикалық тұрғысынан өте үлкен қызығушылық туғызады. Қазақстан Республикасының жағармайэнергетикалық кешенінің даму стратегиясында көмірсутектік шикізат өңдеуіндегі негізгі органикалық синтезге жататын алкандардың синтез-газға дейін тотығу айналымы жаңа технологияны өңдеудегі мұнайхимиялық өндіріс технологияларының кешеніне кіре алады. Бүгінгі күнде табиғи және ілеспе мұнай газдарын орынды пайдалану мәселесіне әсіресе оларды факелдерде өртеулерді тоқтату өткір және шешілмеген экологиялық аһуалдардың бірі болып табылады. Әсіресе дағдарыс кезінде және мұнай қорларының шектелген жағдайында, табиғи және ілеспе мұнай газдарын мұнайхимияның және органикалық синтездің бағалы өнімдерін алуының баламалық қайнар көзі ретінде қарастыруға болады. Соңғы 50 жылда метанның нәтижелі айналу жолдарын іздеу катализдің негізгі бағыттарының бірі болып келеді, бірақ, осы уақытқа дейін, өнеркәсіпте метанның бағалы химиялық өнімдерге тура конверсиясы жүзеге асырылмаған. Табиғи газды өңдеудің бірінші сатысы әрқашанда синтез - газ алу болып табылады, оны әрі қарай өңдеу арқылы одан әртүрлі пайдалы химиялық өнімдерді алуға болады. Синтез-газ - органикалық синтездің бағалы жартылай өнімі. Ол таза Н2 мен СО, аммиак, метанол, диметил эфирі, сірке қышқылы, спирттер мен альдегидтердің өндірісінде, Фишер-Тропш процестерінде, сонымен қатар, қара және түрлі түсті металлургияның қалпына келтіргіш газы ретінде, металл өңдеуде, экологиялық газ өндірісін залалсыздандыруда және басқа көп жүкті процестерде кеңінен қолданылады [1 - 3].

2. Тәжірибе Катализаторлар жүйелі металдар тұздарының сулы ерітінділерінен капиллярлы ылғал сыйғыштық әдіспен ауа тоғында жылыту жолымен әзірленген. Реакцияға дейінгі және ре-

акция соңынан шығатын газ қоспасының құрамы хроматографиялық әдіспен «Хроматэк Кристалл 5000.1» және «Agilent Technologies 6890 N» хроматографтарында талданды. 2%Ce/(θ+α)Al2O3 тасымалдағышына қондырылған 0,05 - 1,0% Pt, Ru және Pt - Ru катализаторларында металдардың әртүрлі қатынасындағы (салм.%) СН4–ның синтез-газға дейін тотығуы 400 минут бойында, Т = 1173 К, V = 9∙105 сағ.-1 жағдайында зерттелді. Процесті жүргізу үшін катализаторды дайындаудың қолайлы жағдайлары табылған. Қолайлы жанасу уақыты (3,0-4,0мс), онда СН4 конверсиясы мен СО мен сутегінің талғамдылығы 100% құрады. Pt:Ru атомдық қатынасы ~2:1 немесе ~1:1 болған жағдайда 100% көрсеткіштер байқалған: СН4 конверсиясы, Н2 мен СО-ның талғамдылығы 100%. Бұл көрсеткіштер катализатор құрамындағы бағалы металдардың пайыздық көлемі ≥ 0,2 салм.% дейін сақталатыны анықталды [4 - 6]. Метанның тотығу процесін, тек қана түйіршіктелген үлгілерде ғана емес сонымен қатар, ұялы блокты тасымалдағыштарда да жүргізу жұмыста қойылған мақсаттардың бірі болды. Сонымен қатар, катализаторлардың ұсақ дисперсті үлгілерінде жүргізілген процестерде қоспадағы метанның мөлшері 1,6 және 2,0% құрады, ал блокты үлгілерді зерттегенде реакция қоспасындағы метанның концентрациясы 4,4% дейін өсірілді. Тәжірибелік әдіспен блокты керамикалық тасымалдағышқа отырғызылған 0,55 ат.% Pt:0,45 ат.% Ru/2%Ce/(θ+α)Al2O3 катализаторында метанның синтез-газға дейін талғамды каталитикалық тотығуы үшін жанасу уақыты 0,36 с (V = 1∙104 ч-1) және 1173 К температурасы тиімді болып табылатыны анықталды. Бұл блокты керамикалық тасымалдағышта талғамды каталитикалық тотығу процесін бастапқы реакциялық қоспа СН4 : О2 = 2 : 1 қатынасында, Т = 1173 К, V = 1∙104 сағ-1, t = 0,36 с және реакцияға түсетін заттардың концентрациясын СН4 : ауадағы О2 : Ar: 1 - 4,4 : 2,2 : 93,4; 2 - 16,0 : 8,0 : 76,0; 3 - 20,0 : 10,0 : 70,0; 4 - 34,0 : 17,0 : 49,0, (%) өзгерткен жағдайда жүргізілді (сур. 1). Блоктағы Pt-Ru/2%Се/(θ+α)-Al2O3 катализаторында метанның бастапқы концентрациясы 4,4% болғанда СН4-ның айналу дәрежесі 59,1% және талғамдылығы бойынша ең жоғары 100% сутегі және СО алу мүмкін екендігі көрсетілді. Процесс кезінде қолайсыз көміртек диоксиді түзілмейді. july - august №4

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Әрі қарай процестің көрсеткіштерін жоғарылату мақсатында блокты керамикалық тасымалдағыштарға белсенді катализаторды қондырғанда байланыстырғыш рөлін атқаратын алюминий оксинитратының орынына алюминий гидроксиді қолданылды.

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Талғамды каталитикалық тотығу (сур. 2) және буоттекті конверсия (сур. 3) процестерінде метанның конверсиясы мен Н2 мен СО талғамдығына көлемдік жылдамдықтың әсерін анықтау үшін 0,2% Pt-Ru катализаторын ұялы құрылымды керамикалық блокты тасымалдағышқа қондыру арқылы Т = 1173 К және көлемдік жылдамдықты 10000-нан 40000 сағ-1 дейін аралықта өзгерту арқылы зерттелді.

Сурет 1. Метанның синтез-газға дейін талғамды каталитикалық тотығу процесінде бастапқы реакциялық қоспаның концентрациясы өзгеруінің катализатордың белсенділігіне әсері (1 – ХСН4, 2 - SH2, 3 - SCO, Т = 1173 К, τ = 0,36 с, V = 1∙104 сағ-1) Сурет 3. Метанның синтез-газға дейін буоттекті конверсия процесінде катализатордың белсенділігіне көлемдік жылдамдықтың әсері (1 – ХСН4, 2 - SH2, 3 – SCO, Т = 1173 К, V = 1 - 4∙104 ч-1)

Сурет 2. Метанның синтез-газға дейін талғамды каталитикалық тотығу процесінде катализатордың белсенділігіне көлемдік жылдамдықтың әсері (1 – ХСН4, 2 - SH2, 3 – SCO, Т = 1173 К, V = 1 - 4∙104 сағ-1) №4 july - august

2 және 3 суреттерде көрсетілгендей талғамды каталитикалық тотығу процесінде (сур. 2) көлемдік жылдамдықты жоғарлатқан кезде метанның конверсиясы 77,0% дан 54,0%-ға дейін төмендеп, ал буоттекті конверсия процесінде (сур. 3) бұл көрсеткіш 90,1 ден 84,1% дейін шамалы ғана өзгереді. Бұл процестер Н2 мен СО талғамдылығы 100% және СО2 түзілуінсіз жүреді. Метанның бастапқы концентрациясы жоғарлаған кезде керамикалық блокты ұялы құрылымды тасымалдағыштарға отырғызылған 0,2% Pt-Ru катализаторын және байланыстырғыш ретінде алюминий оксинитратының орнына алюминий гидрооксидін қолдану, Т=1173К және көлемдік жылдамдық 1 - 4∙104 сағ-1 аралығында метанның талғамды каталитикалық және булыоттекті каталитикалық тотығу процестерінің конверсия және талғампаздық көрсеткіштерін арттыратыны анықталды.


Қорытынды Метанның синтез газға дейін каталитикалық тотығу зерттеулерінен төмен пайызды асыл металдар негізіндегі катализаторларды ұялы құрылымды керамикалық блокты тасымалдағыштарға отырғызған кезде метанның талғамдылығы Н2 және СО бойынша 100% болатыны табылды.

Әдебиет тізімі 1. Исмагилов З.Р. // «Мұнайхимияның өзекті мәселелері» атты III Ресей конференциясы. – Звенигород, 2009. - Б.132-133. 2. Калачева Л.П., Федорова А.Ф. // Мұнай мен газ химиясы атты VII халықаралық конференция. – Томск, 2009. - Б.545-548. 3. Розовский А.Я. // Химияның тұрақты дамуы. - 2005. - Т.13, №1. - Б. 701-712. 4. Досумов К., Попова Н.М., Байжуманова Т.С., Тунгатарова С.А. // ҰҒА Хабаршысы. Химия сериясы. 2009. №3. - Б.15-19. 5. Popova N.M., Tungatarova S.A., Dossumov K., Baishumanova T.S. // Journal of Alloys and Compounds. - 2010. - 504S. S349-S352. 6. Dossumov K., Tungatarova S.A., Baizhumanova T.S. // Topics in Catalysis. 2010. - V.53, №.15. - P.1285-1288.

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july - august №4


УДК 541.64+648.744

MACROMOLECULAR COMPLEXES OF HYDROGELS E. Bekturov1, R. Iskakov2 Institute of High Technologies, Almaty, Kazakhstan, 2 Каzakhstan-Britain Technical University, Almaty, Kazakhstan e-mail: [email protected]

1

Обсуждены результаты исследований интер- и интраполимерных комплексов гидрогелей. Гидрогельдердің интер- және интерполимер жиынтығының зерттеу нәтижелері талқыланды.

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Abstract Results of investigation of inter- and intrapolymer complexes of hydrogels are considered. Keywords: Hydrogels, polymers, complexes, swelling 1. Introduction As well known hydrogels are capable for strong swelling of several tens times in aqueous solutions. Swelled gels may undergo a collapse-like sharp decrease of their volume to reply on some non-essential changes of external conditions, such as temperature, pH, ionic strength, chemical additives, light irradiation, pressure, either electric or magnetic fields [1,2]. Such interest to hydrogel behavior is not simply academic, because of intensively high level of their application in industry, medicine, pharmacy, agricultures and so on [3]. Polymer hydrogels also can drastically change their volume through a complex formation with different additives including another high-molecular substance. The so-called macromolecular complexes of hydrogels may be roughly divided on four major types: 1. Complexes of hydrogels with linear macromolecules or semi-interpenetrating networks; 2. Interpenetrating networks; 3. Intrapolymer complexes of hydrogels on the basis of either graft or block copolymers; 4. The so-called intergel or gel-gel complexes of contact and distant types. №4 july - august

If the first three types of gel complexes have scrupulously studied and descried in various literature, the last type of complexes is just on starting way of investigation. However possible practical uses of such systems could be extrapolated now on their further industrial realization. This paper is generally focused on intergel systems, moreover other types of gel complexes are described here.

2. Results and discussion 2.1 Complexes of hydrogels with linear macromolecules An interaction of linear poly(acrylic acid) (PAA) under 1x105 MM with polyvinylpirrolidone (PVP) gels leads to drastic decrease of swelling coefficient Ks due mainly to a complex formation between linear parts of the gel and PAA stabilized by a system of cooperative hydrogen bonds and additionally by hydrophobic interactions as shown in Figure 1 [4]. In case of PAA with high MM within 2.5 ÷4.5 x105 a decrease of Ks occurs hardly. Perhaps longer molecules of PAA can not penetrate easily into gel volume and complex formation occurs only on the surface of the gel due to steric difficulties. A slight pH change impacts on the gel-PAA complex with its final destabilization. Indeed, the gel-PAA complex exists only at low acidic level below pH 3.6 (Figure 2). Increasing pH provokes Ks increase and gel reswelling is clearly observed due mainly to ionization of carboxylic groups and destruction of hydrogen bonds. The Ks value reaches the initial ratio and manifests destruction of the


systems – either linear sodium polyacrylate and gel of poly-2-methyl-5-vinylpyridine hydrochloride (PMVP); or linear sodium polystyrene sulfonate and gel of PMVP [7,8]. Stability of those complexes is strictly depended on pH or ionic strength range, either dimethylformaldehyde additive concentration.

Figure 1. Dependence of swelling coefficient Ks of PVP gel on PAA concentration with various molecular weight: 1 –4.5x105 , 2 – 2.5x105 , 3 –1.0x105 complex. Typical destruction of polymer-gel complexes is possible also in the presence of some additives such as an organic solvent dimethylsulfoxide (DMSO), which is responsible for both hydrogen bond break-up and decreasing hydrophobic interactions (Figure 3). As shown in the figure a drastic increase of Ks for either the gelPAA or polymer-polymer complexes occurs in a mixture enriched with DMSO upper 50 vol.% due basically to complex weakening.

Figure 3. Dependence of swelling coefficient of PVP-PAA gel complex (1) and intrinsic viscosity of its complex (2) Interpolymer reactions between linear or rare crosslinked PAA with either cross-linked (linear) polyethyleneimine (PEI) or polydimethylaminoethylmethacrylate respectively show strong sense to any pH changes [9]. In order to describe a transportation of linear polyions into oppositely charged hydrogel the so-called relay-race mechanism is appropriately proposed. 2.2 Interpenetrating networks Interpolymer complex formation may be brightly realized in the so-called interpenetrating networks (IPN) including at least two entangled gels of different nature, linear parts of those enable for cooperative interactions. A stark example of IPN contains PMAA and polyethyleneoxide (PEO) gel networks [10]. Formation of a complex occurs at pH below 4 owing to cooperative hydrogen bonding through the chains with final collapse of such IPN schematically depicted in Figure 4.

Figure 2. рН effect on swelling coefficient of PVP gel (1) and intermacromolecular complexof PAA- PVP gel (2) The same behavior is observed for other systems, such as linear PAA in a gel of polyacrylamide (PAAm) [5]. Moreover, it has been shown a practical use of such formation to transform chemical energy to mechanic one [6]. Polyionic complexes formation stabilized by electrostatic and hydrophobic interaction is brightly demonstrated in

Figure 4. Schematic example of IPN formation, for instance PAA-PEO gels at pH ≤ 4 Complex formation – destruction occurs for an IPN system of PAA and PAAm gels at temperature below july - august №4

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and above 20°C due to wavering hydrophilic-hydrophobic balance of hydrogen bonding [11]. However, IPN of PAA and polydimethylacrylamide (PDMA) keeps balance around 70°C due mainly to higher complementary of its hydrogen bonds [12]. 2.3 Intrapolymer complexes of hydrogels Intrapolymer complexes could be formed to hydrogels through either graft or block copolymerization when a main backbone chain on the one hand and graft-branches or blocks on the other hand are different nature. One of the example is a hydrogel of poly(methylacrylic acid) (PMAA) - graft-PEO [13,14]. In the Figure 5 a scheme of such complex formation at pH below 4 is represented due to arising of hydrogen bonds through cooperative mechanism leading finally to collapse of the gels. With pH increasing an ionization of PMAA takes place with drastic increase of Ks. That reflects on destruction of intrapolymer complexes.

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Figure 5. Schematic example of complex formation based on PMAA-graft-PEO at рН ≤ 4 The same phenomenon is typical for a hydrogel system based on PEO-graft-polyisopropylacrylamide (PIPAA) where pH and temperature are affecting parameters [15]. A formation of intrapolymer complexes occurs also at the isoelectric points of some amphoteric hydrogels on the basis of vinyl-2-aminoethyl ether with sodium polyacrylate [16]. With some deviation of pH around isoelectric point the hydrogel complex undergoes destruction due basically to ionization of either acidic or aminogroups. 2.4 Intergel complexes In our work has been shown a possibility of complex formation by interaction of two gels of different nature at their contact sides [17-19]. In Figure 6 a dependence of swelling coefficient Ks on a composition of sodium polyacrylate and polyallylamine hydrochloride is shown. The figure shows a negative deviation of Ks in the presence of some additives. It could be explained as some partial complex formation due to electrostatic interactions of oppositely charged functional groups on the surfaces of hydrogels. Moreover, it is highly №4 july - august

possible a surfacial penetration of linear chains of the hydrogels into each other. Because of small volume of the hydrogels involve in the interaction there is no remarkable contraction in the whole system.

Figure 6. Dependence of swelling coefficient of a sodium polyacrylate – polyallylamine hydrochloride gels on their composition and its additive curve Such behavior between the surfaces of two gels can be demonstrated as shown in Figure 7. Similar results are also obtained for the following systems: sodium polyacrylate – PEI hydrochloride, PAA – PEI, PAA – poly-4-vinylpyrridine (PVPy). The last systems shows remarkable electrostatic interaction between negatively charged carboxylic groups and positively one aminogroups with proton transportation from polyacid to polybase.

Figure 7. Schematic illustration of contact interaction of two oppositely charged gels An effect of additives is clearly manifested as its dependence on Ks ratio for a system of PAA-PAAm gels (see Figure 8). A main reason of the deviation is formation of interpolymer complexes at the boards of hydrogel particles stabilized by cooperative hydrogen bonds as well as additional hydrophobic interactions. Unremarkable deviation of Ks may be due to short linear chains of surfacial area involved in the process. This effect could be increased using longer branch chains on the surface of gels. Recently some works dedicated to intergel interaction are considered behavior in a system between anionic and cationic gels [20,21]. A slight decrease of Ks


is observed in such system comparatively to the initial one with estimated degree conversion within 15-20% range [21]. Thus, some gels of different nature at contact interaction are formed complexes through either electrostatic forces or hydrogen bonding.

at all. A distance effect on Ks shown in Figure 10 does not appear all distance long. However, pH influence on a system of PAA gel (Ks=22) via PEI one (Ks=5) appears with drastic swelling ratio decrease from 50 to 5 at pH below 1.15 due generally to suppressing of PAA gel ionization. As well as a drastic Ks increase occurs at pH above 12.75 up to 100 because of remarkable ionization degree of PAA.

Figure 8. Dependence of swelling coefficient of PAA – PAAm gels on their composition and its additive curve Affecting between two gels located at some distance from each other takes also place in aqueous solution with some additives [22,23]. A first gel of PAA or PMAA is located at the bottom of a cylinder; however a second gel of PEI, PVP or PAAm is placed on a glass filter moveable from top to bottom of the cylinder. That allows varying distance between the gels located at the same volume in order to estimate distance effect on interaction ratio. Effect of ratio components at 8 cm distance between gels as shown in Figure 9 is visible hardly, however a remarkable increase of Ks is observed in the distant presence of the second gel in the cylinder. For instance the initial Ks of PAA is about 22 increasing up to 50 point in the distant presence of PEI (Ks=5). Effect of weak polybase PAAm appearance is lower with Ks increasing up to 33. A reason increasing PAA swelling degree may be linked to additional polyacid dissociation in the presence of proton acceptors of polybase. This effect may be called either “distance interaction” or “distance affect” through proton transportation between polyiones of opposite charges. The same type of proton transportation has been observed between linear PAA and linear PVPy with their complex formation [24]. It could be verified example for some systems consisting of fully charged components such as sodium polyacrylate (Ks=180) via poly-2-methyl-5vinylpyrridine hydrochloride (Ks=42), the Ks of intergels being equal 168 does not change

Figure 9. Dependence of swelling coefficient of gels on ratio of the initial gel components at their distant interaction, where [Х] – PEI or PAAm; [Y] – PAA or PMAA; ◊ – PAA (68) ÷ PEI (5); □ – PAA (45) ÷ PEI (5); Δ – PAA (22) ÷ PEI (5); ○ – PMAA (22) ÷ PEI (5); ● – PAA (22) ÷ PAAm (16), where Ks inside the round brackets.

Figure 10. Dependence of swelling coefficient on distance between two opposite gels: ◊ - PAA (22) ÷ PEI (5), □ – PMAA (22) ÷ PEI (5), Δ – PAA (22) ÷ PAAm (16), ○ – PAA (22) ÷ PMAA (22), where Ks inside the round brackets july - august №4

63


A mechanism of such distant interaction between two opposite charged gels could be considered as the formation of non-compensated electrostatic charges owing to chemical bonding of proton on polybase. As results both gels become extra swelled those occur because of either repulsing of the same charges of a gel or mutual attraction of opposite charged gels. In this case the first assumption is more plausible because the mutual interaction of the gels disappears with growing distant while Figure 10 does not show any distant effect on swelling. An internal repulse of gel due to the same charges formation in the network might be reason of noncompensated charge or monoelectric layer of the gel surfaces Thus, a presence of two gels of different nature at some distance may anyway effect on swelling behavior of each other using additives of a solution as mediator due to the formation of MEL on the surfaces of gels. Commonly, consideration of macromolecular complexes of hydrogels demonstrates wide diversity of their behavior those can be exploited in industry and medicine.

64

3. Conclusion Results of investigation of macromolecular complexes of hydrogels including semi-interpenetrating networks, interpenetrating ones, intrapolymer complexes of hydrogels on the basis of either graft or block copolymers were briefly summarized. A special attention was paid for lack studied types of gel complexes such as gel-gel or intergel interactions. It was shown that complex formation takes place on boards between two unlike gels at their direct contact with partial collapse intertwining of their surfacial side chains. Such complexes might be stabilized through either electrostatic contact or hydrogen bonding leading to hydrophobization of peripheral areas of both gels those could form contracted layers. A new phenomenon of mutual influence of hydrogels located at distance indirectly through a media was described as the so-called distance affect. A system of PAA gel via PEI one manifested remarkable additional swelling due to mutual motivation of gels through ionization of both carboxylic groups of the polyacid and aminogroup of the polybase by proton transportation between them. This fact could be interesting because of possible presence of polyions those loosed partially their co-ions. Thus, consideration of different types of hydrogel macromolecular complexes demonstrated brightly their wide diversity in behavior those could be a subject of interesting practical application. №4 july - august

References 1. Dusek K. (Ed). Adv. Polym. Sci., 1993, V.109 and 110. 2. Bekturov E., Bimedina L., Mamytbekov G. Complexes of water-soluble polymers and hydrogels, 2002, Almaty, 230 p. 3. Suleimenov I., Iskakov R., Batyrbekov E., Zhubanov B., Bekturov E. Hydrogels in pharmacy, 2004, 180 p. 4. Bekturov E., Frolova V., Bimendina L. Macromol. Chem. 1999. V. 200 (2), P. 431-435. 5. Frolova V., Bekturov E., Bimendina L. Izvestia MON RK, Ser. Chem., 2000, V.2, P. 39-45. 6. Osada Y., Saito Y. Macromol. Chem. 1975, V. 176 (9), P. 2761-64. 7. Frolova V., Mamytbekov G., Jumadilov T., Bekturov E. Izvestia MON RK, Ser. Chem., 2000, V.5, P. 22-29. 8. Bekturov E., Frolova V., Mamytbekov G. Macromol. Chem. Phys. 1998, V. 199, P. 1071-73. 9. Kabanov V., Zezin A., Rogacheva V., Litmanovich E. Doklady AN SSSR, 1986, V. 228 (6), P. 1408-11. 10. Nishi S., Kotaka T. Macromolecules, 1985, V. 18 (8), P. 1519-25. 11. Ilman F., Tanaka T., Kokufuta E. Nature, 1991, V. 349, P. 400. 12. Aoki T., Kawashima M., Katono H., Sanui K., Ogata N., Okano T., Sakurai Y. Macromolecules, 1994, V. 27 (4), P. 947-52. 13. Lagutina M., Rykova G., Yarygina N., Dubrovski S., Kazanski K. Vysokomol. Soed. Ser. A. 2002, V. 8, P. 1295-301. 14. Lowman A., Peppas N. Macromolecules, 1997, V. 30 (17), P. 4959-65. 15. Mikosh W., Geissler E. Ber. Bunsen-Ges. Phys. Chem. 1998, V. 102 (11), P. 1589-93. 16. Freinberg Y., Sigitov V. Vestnik KazGU, Se. Chem. 1998, V. 10 (2), P. 61-63. 17. Ismailova S., Jumadilov T., Bekturov E. Vestnik KazNTU, 2004, V. 3 (41), P. 186-189. 18. Ismailova S., Jumadilov T., Bekturov E. Izvestia Kahak, 2005, V.2, P. 67-71. 19. Ismailova S., Jumadilov T., Bekturov E. Izvestia Kahak, 2007, V. 1, P. 33. 20. Kokufuta E., Ogawa K., Miyake M. Proc. 6th Int. Symp. Polyelectrolytes, Dresden, 2006, 24. 21. Karpushkin E., Kechekian A., Zezin A. Vysokomol. Soed. Ser. B, 2006, V. 48, P. 2053-57. 22. Jumadilov T., Ismailova S. Vestnik KazNU, 2005, V. 4, P. 60. 23. Ismailova S., Jumadilov T., Bekturov E. Izvestia MON RK, Ser. Chem. 2004, V. 4, P. 80-85. 24. Lutsenko V., Zezin A., Rudman A. Vysokomol. Soed. Ser. B., 1971, V. 13, P. 396.


УДК 541.18.182

INFLUENCE OF PLASTIFIERS CONCENTRATION ON THE RELATIVE CHANGING OF SURFACE TENSION ON THE BONDERY SOLID – LIQUID K.G. Mukhamedov1, S.S. Khamraev2 1 Tashkent Chemical-Technological Institute, 2 Institute of General and Inorganic Chemistry of Academy of Science of the Republic of Uzbekistan

Было измерено поверхностное натяжение на границе «раствор пластификатора–воздух» (σт-г) и краевые углы смачивания (θ) на отполированной поверхности мрамора (СаСО3), используемого в качестве модельной системы, имеющего близкий к мелу химический состав. Бордың химиялық құрамына жақын келетін, модельді жүйе ретінде қолданылатын «пластификатор ерітіндісі - ауа» шекарасындағы беттік керіліс және тегістелген мәрмәр (СаСО3) бетіндегі аймақтық сулау бұрыштары өлшенді.

Abstract There have been measured the surface tension on border «a plastifier solution - air» (δs-g) and limiting corners of moistening (θ) on the polished surface of a marble (СаСО3), having similar to chalk a chemical composition and using in this investigation as modeling system. СаСО3 surface has been polished, washed out by Na2CO3 solution and then the distilled water for determination of the limiting corner of moistening. Keywords: plastifier, hydrophilization, viscosity, electro conductivity, reological data for this suspension, electro kinetic potential Intensive development of many branches of industry connected with processes of obtain and application of mineral dispersion systems, raising of articles quality, improvement of their physical-technical characteristics, modernization of production and using of new modern technologies at production of materials and articles on their base aren’t possible without fundamental and applied investigations in different fields

of science including chemistry of dispersion systems and surface phenomena’s. Regulation of processes of structure forming, increasing of aggregated stability and achievement of maximal fluidity of concentrated dispersion systems in dynamical and static conditions are actual problems in colloidal chemistry and physical-chemical mechanics. At present time the direct methods of measuring of the surface tension on the boundary solid-liquid are absence and by this reason a changing of δs-l at formation of absorbed layer from molecules of surface-active compounds on the surface of hydrophilic particles of chalk was valued indirectly by changing of the work of moistening (Wm): Wm=δs-g – δt-l = δl-g • cos θ were: δs-g, δt-l and δl-g – surface tension correspondently on the boundary solid-gas; solid-liquid; liquid-gas; θ – limiting corner of moistening. The surface tension on the boundary plastifier solution – air (δs-g) and limiting corner of moistening (θ) on polished surface of marble (CaCO3), having similar july - august №4

65


to chalk a chemical composition and using in this investigation as model system, have been measured. For determination of the limiting corner of moistening on the surface of CaCO3 the it’s sample was polished, than was washed by Na2CO3 solution and distilled water. Drop of solution was polished surface of marble by micro syringe and the limited corner of moistening was determined by method [1]. An average values obtained on the base of 5-7 parallel measuring is presented in Table 1.

As far as the surface tension on the boundary solidgas (σs-g) was constant the fact that increasing of the work of moistening has testified about decreasing of the surface tension on the boundary solid-solution (σs-l) at plastifiers introduction. Decreasing of values of σs-l has testified about hydrophilization of CaCO3 surface. In more degree σs-l has decreased at introduction of WSSASFC that can be explaining by greater content of oxy-groups in aromatic rings of WSSASFC molecules than in molecules of SB-5. Investigations by influence of plastifiers on the electro-kinetic potential of particles of chalk, alumina

Table 1. Influence of plastifiers concentration on the limiting corner of moistening of CaCO3 and surface tension on the boundary solution-air Type of plastifier

WSSASFC

SB-5 66

Measured parameter Corner, degree cos θ δl-g • 103, J/m2 Wm • 103, J/m2 Corner, degree cos θ δl-g • 103, J/m2 Wm • 103, J/m2

0 54,5 0,5807 71,9 41,75 54,5 0,5807 71,9 41,75

Plastifier concentration, kg/m3 0,0625 0,125 0,25 0,5 50,5 49,7 48,3 47,8 0,6361 0,6468 0,6652 0,6717 71,85 71,8 71,75 71,73 45,5 46,74 47,73 48,6 52,5 50,5 49 48,5 0,6088 0,6157 0,6428 0,6626 71,7 71,6 71,3 71,2 43,65 44,6 45,8 46,8

The work of moistening was determined as product of values of the limiting cornе of moistening and the surface tension on the boundary solution-air. The character of concentration influence of the investigated plastifiers on the value of the work of moistening is presented on Figure 1.

Figure 1. Influence of the plastifiers concentration on the work of moistening CaCO3: 1-WSSASFC; 2 – SB-5. №4 july - august

1 46,0 0,6947 71,7 49,61 47,5 0,6756 70,5 47,6

(Al2O3) and silica (SiO2) were carried out with using of method of the potential proceed [2]. The plastifiers additives were introduced in amount 0,1-0,3 % from mass of dispersion phase. Calculation of the electro-kinetic potential was carried out by formula: η • ǽ • ΔΕ ζ= ε • ε0 • ΔР were: ζ – electro-kinetic potential, mV; η – viscosity of dispersing medium Pa•s; ε – relative dielectrical of medium, F/m; ε0 = 8,85 • 10-12 F/m; ǽ - specific electro conductivity, om-1 • m-1. Specific electro conductivity was determined by formula: ǽ = ǽKCl W WKCl were: ǽKCl – specific electro conductivity of the standard solution of KCl; W – electro conductivity of cell with dispersing medium, Om; WKCl – electro conductivity of cell, filled by standard solution of KCl.


The results of investigation are presented in Table 2 and on Figures 2, 3. Table 2. Influence of WSSASFC concentration on the value of ζ – potential Type of disperC, % 0 0,1 0,2 0,3 sion phase P•10-4, - E, mV Pa 0.00 17.2 63.0 70.3 69.8 1.568 18.8 66.0 72.9 72.1 3.136 19.7 69.1 75.5 74.6 4.704 21.0 71.9 77.8 76.6 6.272 22.5 75.0 80.1 78.7 Chalk 7.840 23.8 78.0 82.3 80.5 9.406 25.1 81.2 84.3 82.1 W, mS 0.140 0.227 0.314 0.453 WKCl, mS 1.177 1.177 1.177 1.177 T, 0C 20 20 20 20 -ζ, mV 15.7 59.0 65.5 66.0 -4 P•10 , - E, mV Pa 0.00 8.5 41.3 60.5 65.4 1.568 8.7 41.9 61.2 66.1 3.136 8.8 42.7 62.2 66.9 4.704 8.9 43.5 63.1 67.7 Alu6.272 9.0 44.1 63.9 68.2 mina 7.840 9.1 44.7 64.5 69.0 9.406 9.2 45.1 65.0 69.7 W, mS 0.555 0.622 0.682 0.741 WKCl, mS 1.114 1.114 1.114 1.114 T, 0C 18.5 18.5 18.5 18.5 -ζ, mV 5.8 34.6 47.0 52.0 -4 P•10 , - E, mV Pa 0.00 24.0 39.8 55.5 62.1 1.568 24.7 40.7 56.3 63.1 3.136 25.3 41.7 57.4 64.0 4.704 25.9 42.9 58.3 65.0 6.272 26.5 43.8 59.4 65.9 Silice 7.840 27.0 44.8 60.6 66.9 9.406 27.6 46.0 61.9 67.7 W, mS 0.220 0.371 0.497 0.647 WKCl, mS 1.147 1.147 1.147 1.147 T, 0C 19 19 19 19 -ζ, mV 10.5 29.5 40.1 46.0

Change of ζ – potential is coursed by two factors. Firstly anion active oligomeric additives owing to adsorption on surface of dispersion phase will increase an absolute value of the negative potential of surface. On the other hand as bar as forming of adsorption layer the boundary of sliding will move aside in depth of solution that decreased an absolute value of potential on the boundary of sliding.

Figure 2. Influence of additives concentration on the electro-kinetic potential of chalk particles: 1-WSSASFC; 2 – SB-5; С-3.

Figure 3. Influence of additives concentration on the electro-kinetic potential of alumina particles: 1-WSSASFC; 2 – SB-5; С-3. The second factor has explain for example decreasing of ζ – potential by adsorption of uncharged high molecular compounds both on hydrophilic and both on hydrophobic surfaces; and it has been considered in detail in articles [3,4]. july - august №4

67


Comparison of values of the ζ – potential and reological parameters has shown that in general case the correlation between trend of changing of the electro kinetic potential and reological parameters of investigated systems was observed. Thus for chalk suspensions an addition of plastifiers WSSASFC and SB-5 in amount 0,15% has caused an decreasing τ0 nouth; the plastical viscosity has approached to it’s minimum value. At the same concentrations of oligomers the ζ – potential has increased to its maximal value (from 15 mV to 70 and 65 mV correspondently). Definite correspondence of dependence of value τ0 and ζ – potential for SiO2 and Al2O3 suspensions was observed. At additives concentrations decreasing value of τ0 practically to nought the ζ – potential of suspensions has a maximal value by module. WSSASFC in more degree has increased the absolute value of the ζ – potential that also is correlated with reological data for these suspensions. Equilibrium value of pH for investigated suspensions has changed negligibly (from 7,5 to 8,0) at introduction of plastifiers at 0,3%.

68

№4 july - august

References 1. Savina V.A., Sherbak Y.V. High strong concretes with additives of superplastifiers // Investigation and using of concretes with superplastifiers. – M., 1982. – P.28-32. 2. Kosukhin M.M. Regulation of properties of concrete mixtures and concretes by complex additives with different hydrophilic groups: thesis; cand. techn. scienses:05.23.05 / Belgorod, 1995.-173p. 3. Bedenko V.G. Additive’s carbon-alkali reagent and reological properties of the raw shlam // Concrete, 1989. -№11. P.17-18. 4. Saviskay T.S. Influence of water soluble polymers on stability of reological properties of suspensions of biberous activated carbon. // Colloid Journal. – 2006. – V.68, №1. – P.93-99.


УДК 542.943:547.21:661.727.4

OXIDATIVE CONVERSION OF C3-C4 ALKANES TO ACETONE S.A. Tungatarova D.V.Sokolsky Institute of Organic Catalysis and Electrochemistry, Almaty, Kazakhstan e-mail: [email protected]

Нанесенные полиоксидные катализаторы на основе Мо и W испытаны в процессе окислительной конверсии пропана и пропан-бутановой смеси. Определено влияние температуры реакции, времени контакта, состава и содержания активного компонента катализатора. Mo және W негізіндегі тасмалданған поиоксидті катализаторлар пропа және пропан-бутан қоспасының тотықтыру конверсиясы процестерінде зерттелді. Катализатордағы белсенді компоненттің мөлшері және құрамы, жанасу уақты, реакция температурасның әсері анықталды. 69

Abstract Supported polyoxide catalysts on the base of Mo and W, as well as natural Kazakhstan’s clays were tested in the process of oxidative conversion of propane and propane-butane mixture. The influence of reaction temperature, contact time, composition and percentage of the active component of catalyst were determined. The important petrochemical products acetone (500-550оС) and acetaldehyde (300-350оС) were the main liquid products of reaction on natural Kazakhstan’s clays and also on clays modified by Mo, Bi, Cr, Ga ions. Keywords: Propane-butane, oxidation, clays. Introduction Partial oxidation of liquefied oil gas into ketones and aldehydes is important both in ecology and economy because 10 billion m3 of casing-head gas is burned every year in the world and harmful exhaust into atmosphere measured by thousands of tons. Combustion process by means of huge consumption of oxygen and heat emission promotes strengthening of hotbed effect. The cost of 1000 m3 of oil gas is about $30. Thus economy lost the great sum heating sky. More expensive product than raw substances is possible ob-

tain from oil gas [1,2]. The rapid development of the petrochemical industry in the last decade has raised acute problems of the optimal choice of feedstock and catalysts for relevant processes. According to forecasts for the near future, saturated C1-C4 hydrocarbons not only will retain but also will strengthen their position as a raw material for the production of unsaturated hydrocarbons. Therefore, the problem of searching for ways of their effective conversion into different oxygen-containing compounds is also urgent. Unlike methane and ethane, which yield less complex compounds, propane and butane are expected to give unsaturated hydrocarbons, aldehydes, acids, and alcohols. Only the optimal choice of catalysts can ensure targeted synthesis with the predominant formation of a desired compound selected from these products. Heterogeneous catalysts that are examined in the propane and butane oxidation reactions are represented by both individual [3,4] and mixed oxides [5,6], as well as by catalysts supported on different carriers, including zeolites [7-9].

Experimental The experiments were carried out at atmospheric pressure, 300-600oC, W=300-15000 h-1 in a continujuly - august №4


ous-flow unit with a fixed-bed quartz-tube reactor. The gas mixture used for oxidation contained propane and oxygen in a 1:2 ratio, as well as C3H8-C4H10 mixture (1480%) and oxygen (4-18%) in different ratios. As catalysts, we used a) 1-10% Mo, Cr, Ga polyoxide catalysts with different composition and ratio supported on Torgai natural white clays (NWC) with kaolin structure and with admixture of hematite and α-quartz were dried at 120oC for 5 h and calcined at 300oC in air [10,11], b) heteropoly compounds (HPC) of Mo and W with the Si and P central atoms deposited on supports by the incipient wetness technique followed by calcination at 120oC for 5h in air. The heteropoly compounds were synthesized according to procedures described in [12,13]. An Agilent 6890N gas chromatograph equipped with an FID and TCD was employed for the on-line analysis of the products. The catalysts were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD) analysis, and their surface area, porosity, and elemental composition were determined. Phase structure

of catalysts was recorded on DRON-4-7, operating at 25kV and 25 mA and employing Co-Kα radiation, covering 2ө between 5 and 80o. Morphology, particles size, chemical composition of initial and worked out catalysts for 56 hours were performed on TEM-125K with enlargement up to 133000 times by replica method with extraction and micro diffraction. Carbonic replicas were sputtered in vacuum universal station, and carrier of catalysts was dissolved in HF. Identification of micro diffraction patterns were carried out by means of ASTM cart index (1986).

Results and discussion It was shown that conversion of propane-butane mixture proceeds with the formation of gaseous and liquid products. Partial oxidation of propane-butane mixture with varying the catalytic mixture composition and the contact time yielded acetone, methyl ethyl ketone, methanol, acetaldehyde, croton aldehyde, butanol, and acetic acid, as well as C2-C3 unsaturat-

Table 1. Oxidation of propane over 10%Na3PV7W5O40/aluminosilicate. С3Н8 – 5%, О2 – 10%, N2±Н2О = 85%.

70

С 3Н 8/ Н2 О 1:0 1:7,5 1:0 1:7,5 1:0 1:7,5 1:0 1:7,5 1:0 1:7,5 1:0 1:0 1:7,5 1:0 1:7,5 1:0 1:7,5 1:0 1:7,5 1:0 1:7,5 1:0 1:7,5

Contact time, s

T,оС

1

500

1

550

1

575

1

600

1

625

1

650

0,4

500

0,4

550

0,4

575

0,4

600

0,4

625

0,4

650

5,9 3,6 22,6 14,6 48,2 24,3 64,0 35,8

С2Н 4 0 0 1,1 0,7 2,7 0,6 3,4 1,1

Selectivity, % С 3Н 6 37,5 42,7 31,3 52,9 18,2 34,1 11,9 28,9

72,9

3,4

9,9

4,9

2,5

7,2

3,6

59,3 76,9 3,4 3,8 8,3 17,1 16,3 16,6 25,4 35,9 42,7 35,1 57,1 50,1

1,7 3,4 0 0 0 1,2 1,7 2,2 1,4 2,7 3,3 1,5 4,8 4,6

15,1 10,6 65,9 40,9 45,9 34,6 36,3 34,0 31,4 23,3 20,1 29,7 14,8 20,8

3,9 1,9 26,4 22,8 25,0 16,2 16,9 27,1 16,2 15,0 11,8 13,6 9,2 8,3

1,0 2,6 0 0 0 0,2 0.3 0,4 0,4 1,0 1,4 0,5 2,7 2,3

8,9 8,1 2,3 1,5 3,8 5,9 5,9 5,7 7,9 8,4 8,6 10,4 8,5 10,4

2,3 1,4 0,9 0,9 2,1 2,8 2,8 4,5 4,1 5,4 5,0 4,8 5,2 4,2

CС3Н8

* - oxygen-containing compounds. №4 july - august

OC 25,5 56,5 10,6 25,9 7,8 22,0 4,9 10,4

С2 Н 4 0 0 0,3 0,1 1,3 0,2 2,2 0,4

Yield, % С 3Н 6 2,2 1,5 7,1 7,7 8,8 8,3 7,7 10,3

OC* 1,5 2,0 2,4 3,8 3,8 5,4 3,1 3,7


ed hydrocarbons. The results of propane oxidation on granulated catalysts made of PVW-HPC derivatives showed that the homogeneous oxidation of propane practically did not occur. The propane conversion (C) on the pure support is higher, and the use of catalysts sharply increases the conversion over the entire range of temperature. The main products are oxygen-containing compounds (mainly acetaldehyde), propylene, ethylene, and CO. The addition of water vapour decreases the propane conversion but increases the yield of olefins and oxygenated compounds over practically the whole range of temperatures (Table 1). The increase in the contact time by a factor of 2,5 reveals that the selectivity and their yield become somewhat lower with an increase in temperature, but the yield of CO increases. This is explained by the fact that the products of incomplete oxidative dehydrogenation and oxidation are further oxidized to CO and CO2 at a longer contact time. The promotion of the catalysts with alkali or alkaline-earth metal salts increases the yield of ethylene. The admixture of water vapour significantly increases the rate of the process. For the oxidative conversion process, we also developed polyoxide low-metal-loading catalysts on the basis of molybdenum and tungsten HPC on monolithic (cordierite) supports. Cordierite, SiO2, zeocar, Al2O3, and aluminosilicate were used as the second supports. Zirconium and SiO2 were introduced as stabilizing additives in order to decrease the volatility and to stabilize the structure. The technology of deposition of polyoxide compounds on a porous block by varying the secondary support, the binder, and the protecting layer was developed. Figure 1 presents data on the yield of acetaldehyde plotted against the temperature of the reaction over monolithic catalyst specimens. The Mg salt of SiMo heteropoly acid deposited on the cordierite block with a cordierite secondary support turned out to be the most active. It was found that supported Ni-containing HPC were optimal for the synthesis of hydrogen-rich hydrocarbon mixture. The yield of H2 in the oxidation of a propane-butane mixture was 60-64%. It was found that there were two temperature ranges for the formation of hydrogen and C2 hydrocarbons, which are determined by the occurrence of the oxidative-dimerization and cracking processes. The optimum contact time for the synthesis of H2 and C2H4 is 0,45-0,9s; T=800-900oC at the ratio of C3H8-C4H10:O2=20:1 and the minimum content of water vapour in the mixture. The tests on Torgai natural white clay (the base phase is kaolin Al2[OH]4Si2O5 (ASTM-29-1488) and

Figure 1. Dependence of the acetaldehyde yield on the reaction temperature in the oxidation of a propane-butane mixture on different monolithic catalyst specimens (1) 5,5% Mg2SiMo12O40/cordierite/cordierite, (2) 5,0% Mg2SiMo12O40/cordierite/cordierite with the secondary support stabilized with Zr, (3) 4,9% MgSiMo12O40/cordierite/cordierite, with a Zr protective 2 layer, and (40 5,0% Mg2SiMo12O40/cordierite/cordierite with a SiO2 protective layer. α-quartz (SiO2)), as well as Torgai natural red clay, which differs from the white clay by the presence of hematite (Fe2O3) and the absence of α-quartz (less than 1%) showed that investigation in this direction is interesting also. The treatment of clay specimens with hydrochloric acid slightly changed their phase composition. The specific surface area and porosity of the sorbent specimens examined were determined by the Brunauer-Emmett-Teller low-temperature nitrogen adsorption technique. It was found that the clay surface area is 10-16 m2/g and that the optimum pore radius ranges from 20-50 Å. The treatment of sorbents with 10% HCl facilitated the development of pores and an increase in the pore radius. The elemental analysis of the initial sorbent specimens and those treated with 10% HCl showed that the clay specimens predominantly contained oxide compounds of Si and Al, as well as Ca, Mg, Fe, and Na. Up to 20 other elements in amounts from 0,0008 to 0,4% were found as concomitants. The SiO2/Al2O3 ratio (silica modulus) was 5-0,4. The silica modulus increases after acid treatment. The multi-peaked character of change in the catalytic properties during the oxidation of propane-butane mixture and the highest activity of low-loading supported catalysts are due to the existence of both crystalline and amorphous phases of heteropoly acids on the supports and to the appearance of strong interaction in the heteropoly acid-support system [14]. Combination of TPR and IRS data indicate on formation of a new july - august №4

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type of structure, caused by interaction of HPA fragments with carrier (for example, Si-O-Mo) together with amorphous structure of HPA in low-percentage supported catalysts. This interaction results in change of binding strength of catalytic oxygen and their reactivity concerning H2 and CH4. Important petrochemicals, such as acetone (500550oC) and acetaldehyde (300-350oC) are main liquid products. Ethylene is the main product of gas phase. Yield of ethylene increases beginning from 450oC. The investigation on influence of the nature of carrier on yield of acetone from reaction temperature was carried out. It was shown that more high yields of acetone were produced over NWC. Мо, Cr and Ga samples have shown more optimal properties during investigation of the series of monometallic (Mo, Ce, Bi, Cr, Ga, Fe, Mn, Ni, Co and Zn) supported over NWC catalysts. Ternary catalyst is more active than two-component samples. Investigation of 1, 5 and 10% MoCrGa/NC has shown that 5% sample is active in forming of ketones (acetone, methyl ethyl ketone), 10% - acetaldehyde and 1% - ethylene. The yield of acetone was increased from 32% at 400oC to 50,9% at 550oC, W=450h-1, C3C4:O2:N2:Ar=5:1:4:5 over 5%MoCrGa/NWC (Figure 2). Optimal space velocities for catalysts with different content of active phase over carriers were determined. Up to 23% of acetone and 35% of methyl ethyl ketone on 1%MoCrGa/NWC were produced at W=1350h-1. Increase of content of acetone up to 31% in catalyzate was observed at reduction of propane-butane in reaction mixture. Dependence the yield of acetone from temperature at the different space velocity over 5% MoCrGa/NWC has shown on Figure 3. It was shown that more high yields of acetone were obtained at W=300-450h-1 at 350-550oC. The determination of the product composition showed that the process follows a complex mechanism including oxidation, oxidative dehydrogenation, and cracking. Modification of carrier by zeolite ZSM-5 in the presence of aluminium oxinitrate promoted increase the content of acetone in catalyzate up to 70-80%, but decreased the content of acetaldehyde, Figure 4. The content of acetone was higher the whole temperature interval. C3-C4:O2 ratio was varied in wide interval. C3C4:O2=33,3:7,0 ratio is more optimal for selective obtaining of acetone and acetaldehyde. Large particles and aggregates from large dense particles are characteristic for initial MoCrGa/NWC catalyst. Micro-diffraction picture of particles is submitted by the separate rare reflexes referred to Cr2O3 (JCPDS, 6-508), CrO (JCPDS, 6-532), and also translucent la№4 july - august

Figure 2. Dependence of the acetone yield on the reaction temperature in the oxidation of a propane-butane mixture. С3-С4:О2:N2:Ar=5:1:4:5; τ=8s; W=450h-1. 1- 1%MoCrGa/NWC; 2 - 5%MoCrGa/NWC; 3 - 10%MoCrGa/NWC.

Figure 3. Dependence the yield of acetone from temperature at the different space velocity over 5%MoCrGa/NWC. C3-C4:O2:N2:Ar=33,3:7,0:26,4:33,3.

Figure 4. Influence of the temperature on content of acetone in catalyzate at oxidation of propane-butane mixture. С3-С4:О2:N2:Ar=33.33%:7,0%:26,0%:33,67%. W=1350h-1. 1 - 1%MoCrGa/NWC; 2 - 5%MoCrGa/NWC; 3 - 10% MoCrGa/NW; 4 - 5%MoCrGa/NWC+ZSM-5 + Aln(OH)3n-1NO3.


mellar type a particle, micro-diffraction picture from which is submitted by the reflexes which are settling down on hexagonal motive, referred to CrMoO4 (JCPDS, 34-474). For the Мо-containing phase processed in reaction conditions the dense large crystals (500-1000 Å) with attributes of rectangular motive the facets corresponding Mo4O11 (JCPDS, 13-142) are characteristic. For a Cr-containing phase the large translucent lamellar particles of α-Cr2O3 (JCPDS, 6-503), small congestions made from disperse particles in the size ~ 30Å, referred to Cr2O5 (JCPDS, 36-1329), aggregates from translucent particles with the minimal sizes 200-400 Å and more, characteristic for CrO2 (JCPDS, 9-332), congestion of translucent lamellar particles of Cr5O12 (JCPDS, 18-390) in the size 300-600 Ǻ with rectangular motive of a facet are characteristic. Besides small congestions, characteristic for the joint phases consisting of particles in the size 30-50 Ǻ and large lamellar particles are found. Micro-diffraction is submitted by a mix of rings and separate reflexes. Rings correspond to a phase of disperse particles of CrMoO4 (JCPDS, 29-452), and large lamellar crystals correspond to Cr2MoO6 (JCPDS, 33-401). For a Ga-containing phase the various phases for oxidation of Ga down to a metal phase are characteristic: α-Ga2O3 (JCPDS, 6-503), φ-Ga2O3 (JCPDS, 20-426), ε-Ga2O3 (JCPDS, 6-509) in a mix with Ga (JCPDS, 31-539), Ga (JCPDS, 25-345). Comparison with EМ pictures of initial samples of catalysts has allowed to determine, that as a result of their processing in reaction conditions there is the new phase Cr2O5 corresponding to transition Cr2 + and Cr3 + into Cr5 +, and also joint phases of Мо with Cr in various valent conditions. The physical sense and role of them should be determined.

Conclusion The determination of the product composition showed that the process follows a complex mechanism including oxidation, oxidative dehydrogenation, and cracking. The optimal conditions for synthesis of products were detected: • 50,9% of acetone was produced on 5%MoCrGa/NWC catalyst at 550oC and W=450h-1 in reaction mixture С3-С4:О2:N2:Ar=5:1:4:5; • 41,0% of acetaldehyde was produced on 10%MoCrGa/NWC catalyst at 450oC and W=450h-1 in reaction mixture С3-С4:О2:N2:Ar=5:1:4:5; • 80,0% of methyl ethyl ketone was produced on 5%MoCrGa/NWC+ZSM-5+Aln(OH)3n-1NO3 catalyst at 450oC and W=3150h-1 in reaction mixture С3С4:О2:N2:Ar=1:1:4:1;

• 71,4% of ethylene was produced on 1%MoCrGa/NWC catalyst at 450oC and W=450h-1 in reaction mixture С3-С4:О2:N2:Ar=5:1:4:5; • 83,0% of benzene was produced on 1%MoCrGa/NWC catalyst at 550oC and W=750h-1 in reaction mixture С3-С4:О2:N2=7:1:4. This screening study aimed at searching for appropriate compositions and technological parameters of the oxidative conversion of propane and the propane-butane mixture show that the chosen line of research is promising and makes it possible to obtain good results in the synthesis of hydrocarbons and oxygenated compounds. References 1. Udalova O.V., Shashkin D.P., Shibanova M.D. and Krylov O.V., Catalysis in Industry 6 (2007) 3. 2. Massalimova B.K., Tungatarova C.A., Dossumov K. and Kuzembai K.K., Chemical Journal of Kazakhstan 4 (2006) 133. 3. Danilova I.G., Paukshtis E.A., Kalinkin A.V., et al., Kinet. Katal. 43 (2002) 747. 4. Chen Ming-shu, Weng Wei-Zheng and Wan Hui-Lin, J. Mol. Catal. 14 (2000) 6. 5. Harrison P.G., Bailey C. and Azelee W., J. Catal. 186 (1999) 147. 6. Feng Ling-Yun, Qiu Jin-Heng, Lin Ming, and Xu BoLian Chen Yi, Huaxue xuebao 60 (2002) 1006. 7. Erofeev V.I., Trofimova A.S., Koval’ L.M. and Ryabov Yu.V., Zh. Prikl. Khim. (St. Petersburg) 73 (2000) 1969. 8. Khodakov A., Olthof B., Bell A.T. and Iglesia E., J. Catal. 181 (1999) 205. 9. Choudhary V.R., Mantri K. and Sivadinarayana C., Micropor. Mesopor. Mater.: Zeolites, Clays, Carbons, Relat. Mater. 37 (2000) 1. 10. Dossumov K., Tungatarova S.A., Kuzembaev K.K. and Massalimova B.K., Petroleum Chemistry 45 (2005) 261. 11. Dossumov K., Tungatarova S.A., Kuzembaev K.K. and Massalimova B.K., Izv. NAN RK, Ser. Khim. 5 (2004) 70. 12. Pope M.T., Heteropoly and Isopoly Oxometalates (Springer, Berlin, 1983; Nauka, Novosibirsk, 1990). 13. Handbuch der praporativen anorganischen Chemie, Ed. By G. Brauer (Ferdinand Enke, Stuttgart, 1981; Mir, Moscow, 1985). 14. Tungatarova S.A., Savelieva G.A. and Dossumov K., in: Proceedings of NATO Advanced Study Institute. Sustainable Strategies for the Upgrading of Natural Gas: Fundamentals, Challenges, and Opportunities, Vilamoura, Algarve, Portugal, 2003, 345. july - august №4

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MAKHMUD KASHGARY (1029/391101) - THE OUTSTANDING CENTRAL ASIAN PHILOLOGIST OF THE XI CENTURY A.S. Beisenova Abay Kazakh National Pedagogical University

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akhmud Kashgary, Makhmud ibn alHussein ibn Mohammed - the great scientist, one of outstanding Central Asian philologists of the XI century, the author of the first Turkic dictionary. He is the native of barsagan family, Karakhanid dynasty, the grandson of Karakhanid’s conqueror Maverannahra Bogra khan. His father operated the Balasagun city. He has got education in Kashgar, continued in Bukhara and Bagdad. He has received knowledge on jurisprudence, arithmetic, the Koran, Sheriyat and khadis, studied the Arabian-Persian languages, literature and culture. In Bagdad belonging at that time seldzhuks, Kashgary №4 july - august

has decided to write the book in which the explanation of many aspects of life of the Turkic people would be given, its mentality, customs, moving geography, and first of all language. In the XI century he has written the treatise «Divan lugat at-turk» and raised the status of Turkic languages. In the transactions, consisting of three volumes and 8 books, 6800 Turkic words are scientifically systematized. Well-known Makhmud Kashgary’s book «Divan lugat at-turk» represents the Turkic encyclopedia. The extensive historical and cultural, ethnographic and linguistic material is collected and generalized in it. «Divan lugat at-turk» - the monument of the Turkic culture which have embodied ethical values and standards of behavior, specific attitude of the Turkic people in the XI century. In the book along with ancient Zoroastrian-shamanist perception of world had been embodied elements of new ideology of Islam and such branch as sophism. Makhmud Kashgary wrote about the book: «I have compounded this book in alphabetic order, decorated its by proverbs, sadzhs (rhymed prose), by-words, verses, radzhazes (verses of the aggressive content) and fragments from prose. I have facilitated difficult, explained vague and worked for years... Together with it I have collected in the book mentioned subjects and known words; the book was raised to high dignity and has reached the excellent superiority». By M. Kashgary, the person should aspire «to virtue, acquiring it not to be proud». M. Kashgary sees all angrily in narrowmindedness. «Things and property of the person are his enemies... All people have deteriorated because of thing. Having seen property, they rush on it, as if a griffon on bag... They keep the property, having locked it, do not use, crying from sparseness, they collect (save) gold». M. Kashgary’s «Divan lugat atturk» is a unique monument of Turkic dialectology of


the early Middle Ages. The scientist for the first time in history of turkology has used an historic-comparative method, created the base of dialectology. Keeping features of Turkic tribes, he used proverbs and sayings at the description. He uses in the dictionary ethnonyms, toponyms, names of related relations, clothes, designations of traditions and ceremonies of 29 tribes, describes symbols even small families. The round map of the scientist is known as the most ancient Turkic map in which places of moving of Turks are specified. The book has been finished in Bagdad (1072-1078). In 1997-1998 it has been published for the first time in the Kazakh language. M. Kashgary is also the author of the treatise «Kitap-i-dzhavahir annakhv fi liga tat-turk» («About valuable qualities of syntax of Turkic languages»). But the book has not remained. Being younger contemporary of Jusuf Hass Hadzhib Jusuf Balasaguni, Kashgary has entered into studying of languages a comparative method and the historical approach, having put in pawn bases of that nowadays we name turkology. Al-Faraby was predecessor Kashgary. Al-Faraby works formed a basis for al-Biruny works. Turkic names of medical products at Biruny and at Kashgary are the same. Kashgary had both fine Arab-philological education and knowledge of all areas of a medieval Muslim science. «The dictionary of Turkic adverbs», devoted to Caliph al-Muktadi, has been made by Makhmud Kashgary in 10721074. He has presented the basic genres of Turkic folklore - ceremonial and lyrical songs, fragments of the heroic epos, historical legends (about Alexander the Great campaign), more than 400 proverbs, sayings and oral sayings. Makhmud Kashgary’s “Divan” (“Dictionary”) - a unique monument of Turkic dialectology of the early period, giving representation about the phonetic and morphological phenomena and specificity of dialect forms. “Dictionary” contains also texts of orally-poetic creativity of Turkic tribes and the people of Central Asia, East Turkestan, and the Volga region. Makhmud Kashgary’s work written with application of scientific methods of the Arabian philology has and today exclusive value for philologists, specialists in folklore and literary critics. Makhmud Kashgary wished to prove, that value of Turkic language is not smaller, than Arabian. For the first time the manuscript «Divan lugat at-turk » was bought by Turkish scientist Ali Amiri on a market in 1914-1915. He has charged to put in order manuscript to Kilasly Rifat. Rifat has made a copy of work

and has published in 1915 the first and second book, and in 1917 - the third book in Istanbul. Since then versatile research of work begins. Many scientists were engaged in language research, the text edition. For example, Brokkelman К. has resulted word-combinations in conformity with alphabetic order and published translations into German. Turkish scientist Basym Atalaj in 1914 has translated into Turkish and published a three-volume edition in Ankara in 1934-1943. In 1960-67 scientist Mutalibov С. has translated work into the Uzbek language. Then the work was published in China into Uigur. M. Kashgary’s work contains many valuable data on economic, material, spiritual position of Turks. This work contains valuable data in the field of the literature, geographical and astronomical data, features of language and scientific researches. Academician Kononov I.A on coverage of materials subdivides «Divan» into 5 branches: 1. A lexicon of certain families; 2. Data on a site of the families of Turkis; 3. Grouping of Turkic languages; 4. Data on historical phonetics and grammar; 5. Data on history, geography, ethnography, poetry and folklore of Turkis. Makhmud Kashgary has laid down the aim: to consider the words belonging only to Turkic language. Therefore we meet in the dictionary the words designating clothes, house utensils, agricultural production, the weapon, musical instruments, related and breeding names, ranks, names of dishes, animals, vegetation, names of days, months, cities, illnesses, medicines, games. Kashgar was large shopping centre on the Great Silk way. The great scientist has grouped 6800 Turkic words in the book (110 names of the earth’s and rivers, 40 nationalities and tribes), given the explanatory in the Arabian language. 242 poems, 262 proverbs and sayings are resulted in the book. It is surprising that entered in «Divan» 875 words and 60 proverbs and sayings without any changes have entered into the Kazakh language. Makhmud Kashgary was the witness of unknown military triumph of Turkis on huge space of a Muslim civilization of XI century. At this time the Turkis, hitherto known to the world basically as hired soldiers in armies of Muslim governors, under control of Seldzhuk’s dynasty have subordinated to themselves the extensive territories which were under the control of the Arabian and Iranian dynasties from Khurasan to the Mediterranean in the Near East, and also Asia Minor, july - august №4

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having won over the Byzantian emperor. In the end of the Х centuries east Turkis under control of Karakhanid dynasty where Kashgar was the main city, have confirmed the power in Central Asia, having won over Samanid dynasty. “Divan” was created in the Arabian language as the encyclopedic dictionary acquainting readers with language and culture of Turkic conquerors, come to power on the basic part of caliphate. The maintenance of „Divan” clearly testifies that for Kashgary there was no conflict between Islam and pre-Islamic Turkis faith. Kashgary absolutely naturally translates on the Arabian the numerous Turkic citations with a mention of a name of god Tengri. It is unknown, whether has finished Kashgary the initiative up to the end, that is whether he has presented the work to the Caliph as it was spoken in its foreword. That manuscript which has reached up to now, concerns to the XIV century. This manuscript has been found again in 1916 or 1917 in Turkey, having made the big effect in the intellectual world. It has appeared on one of the book markets in the second decade of the XX-th century and since then has entered into scientific use. Zifa-Alua Auezova, the Candidate of Philological Sciences, orientalist, granddaughter of the classic of the Kazakh literature, has devoted to transfer of a unique monument of culture of ancient Turkis Makhmud Kashgary “Divan lugat at-turk” more than 3 years. Work on transfer has begun at the initiative of Fund “Soros - Kazakhstan” in 1999 and some years lasted as besides transfer of the volume hand-written text it provided also research of some interesting problems. First of all is a studying of a lexicographic material from “Divan lugat at-turk”, entered into earlier researches and dictionaries. It is published in 1972 in the Great Britain Klozen’s “The Etymological dictionary of Turkic language till XIII century”, “The Ancient Turkic

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dictionary” published in 1969 by Linguistics Institute in Leningrad, and other editions on which it was necessary to verify a transcription and interpretation of separate Turkic lexemes. The help of Zifa-Alua Auezova’s relatives in work on transfer of “Divan lugat at-turk” was invaluable. Her husband Robert Ermers, the Netherlands scientist specializing on history of Turkic and Arabian linguistics, edited transfers. Mum Horlan Matenovna Rahimbek, the researcher of philosophy of natural sciences and education, took active participation in editing of Russian part. She is the fine stylist and the judge of the literature. The daddy Murat Auezov, the orientalist and the culturologist, was the inspirer of work on transfer from its most beginning. During this period he has visited Opal (China) where presumably there is Makhmud Kashgary’s burial place. This district since ancient times is famous for the pottery. He has brought daughters to Holland a jug from Opal, which clay, probably, stores memory about Makhmud. “Divan” completely was not translated on Russian. The big material from it was included into “The Ancient Turkic dictionary”, published in 70th years by Institute of linguistics of the Academy of sciences of the USSR. Separate lexemes from “Divan” were considered in it, but the considerable part of a cultural and linguistic material has been lowered. Why it is important to have transfer in Russian? Now people, associated themselves with Turkic culture, live on huge space of the former Soviet Union, well know Russian and got education in Russian. It is language of a science and culture which unites generation of researchers for today both in Russia, and in the countries of the Central Asia. In this region the people who well know Russian, could estimate and well experience this monument. This translation into Russian can be the important source for research work of historians and literary critics.

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