PROSPECTIVE FUNDAMENTAL RESEARCH IN THE SPHERE OF CREATING NEW PROCESSES IN PETROLEUM AND GAS CHEMISTRY
The development of new highly-efficient, energy-efficient and resource-conserving, environmentally-friendly technologies in petroleum and gas chemistry, hydrocarbon production and their treatment, production equipment for these purposes have always been based on fundamental research. The relevance of fundamental and applied research considerably increases in the context of modernization of the Russian economy, transition from the resource orientation to high-level processing products with high added value. It determines the increasing role of scientific and technical potential of the Russian Academy of Sciences in the development of the national innovation system. And, currently, Russian Academy of Sciences has joined major state programs, technological platforms, including those aimed at modernization and development of such an important branch of economy as oil industry.
To accelerate the transition of oil-refining and petrochemical industries to a crucially new stage of development, Institutes of the Russian Academy of Sciences are planning to do some research to develop conceptually new technologies of refining carbonaceous feed, especially concerning development of technologies of advanced processing of carbonaceous feed for motor fuels and raw stock for petroleum chemistry, processing of natural and associated gases into synthetic gas and olefines, creation of membrane and membrane-catalytic processes to get new polymeric materials. It's important to note the decisive role of application of catalytic technologies in the vast majority of petrochemical processes. Therefore, a lot of attention is paid to the creation and research of new catalyzers.
The set of operations to develop scientific basis of modern processes of production of essential chemical and petrochemical products, utilization of associated and reformed gases, production of polymeric materials with a new property package, synthesis of nano-materials and catalyzers is carried out in the Institute of problems of chemical physics of the Russian Academy of Sciences. Besides, purely fundamental research, the Institute, possessing a unique chemical and technological complex, can test new processes on model and pilot plants, to make their technical and economic assessment and commercialization.
There is already a solid scientific reserve and further development of fundamental research and improvement of the technology of oligomerization of olefines with production of the base of synthetic oils (PAOO - polyalphaolefin oils). The proposed method of preparation of poly-alpha-olefins has a number of advantages. As a result of conducted funda mental research and applied developments, the first in the Russian industry original process of preparation of oligodecenes of various application was launched at Nizhnekamsk plant of synthetic oils with an output - 10 000 tons of PAOO a year. Relatively low output of the first production of PAOO in Russia (with the demand of the Russian consumers of 200 000 tons a year) is explained by limited resources of decene -1 - an ideal raw product for this process. The increase of the output of PAOO production and it replication by other enterprises is possible only on the basis of expansion of the olefin base of the process. Meanwhile, it also demonstrates the possibility of producing high quality PAOO by cooligomerization of mixes of octene-1, decene-1, dodecene-1 and tetradecene-1 in accordance with the abovementioned base technology.
For this purpose, Institute of Problems of Chemical Physics of the Russian Academy of Sciences carries out original research and developments aimed at the creation of fundamental scientific base and technological support of selective catalytic processes of preparing individual high olefin from the available oil stock and renewable vegetable feed, which have a limited consumption. The solution of the problem is achieved in the following ways:
• Development of the method of selective synthesis of decene-5, dodecene-6 and tetradecene -7 by way of metathesis of hexene-1, mixes of hexene-1 with octene-1 and octene-1, catalytic systems MoO3/SiO2 + AlR3 or MoO3 /Al2O3 + AlR3;
• Research of the process of preparation of izoolefins С6, С8, С10, С12 and С14 by means of catalytic synthesis of the above izoolefins by the reaction of high alpha-olefins С4-С12 with (C2H5)nAlCl3-n in the presence of zirconium compounds;
• Refinement of a two-stage process of production of decene -1 and other high olefins by way of ethenolysis of methyl ethers of oleic, linolic and linoleic acids under the influence of highly-active and high-performance catalytic systems.
• Development of method of catalytic hydrogenation to improve the quality of PAOO to the level of world standards. Besides the process of PAOO production, the above method is quite perspective in the development of original technologies of hydraulic cleaning and hydroisomerization with application of suspended catalyzers.
One of the most important activities is the creation of new catalytic systems of olefins polymerization and study of their action mechanism. It was demonstrated that in case of polymerization of ethylene with application of catalytic system Cp4Zr - МАО - Ti(OBu)4 it is possible to exclude additions of comonomer and production of linear low density polyethylene. The process of the system performance includes two catalytic cycles: the first cycle is a production of butene-1 from ethylene of high selectivity, while the second includes interpolymerization of ethylene with synthesized butene -1 under the effect of Cp4Zr - МАО. Thereupon, the new improved process of production of high, medium, and low density polyethylenes was proposed, which is characterized by a number of advantages in comparison with the existing analogues. The developed catalytic systems possess the highest parameters of catalytic activity (up to 2.5 tons of product, on the basis of 1 gram of zirconium per hour), they are characterized by the simple method of their creation. The process of production of the whole branded assortment of polyethylenes using as a feedstock only ethylene (without comonomers) with uni-column process.
The crucially new, having no world analogues, way of production of especially clean foamed polystyrene looks quite perspective. The base includes a high-performance method of frontal polymerization, which allows entering the initial monomer carbon dioxide, which, in the process of polymerization, together with residual monomer, passes to a supercritical state. The whole process - from monomer to finished product - occurs in a single closed manufacturing chain. There have been obtained samples of foamed poly styrene in a wide range of values of apparent density (15-85 kg/m3) with low content of residual monomer (less than 0.1%). The results of the conducted research are a scientif ic basis for subsequent development of energy-conserving, environmentally safe technology for production of extra pure polymers for optical fibers, as implants in medicine, biological preparations of prolonged action etc. It should be noted that the synthesis of polymeric materials and polystyrenes (foam plastics) in the mode of frontal polymerization also gives an option of making large-size polymer glass, having a complex geometric form and high optical and mechanic properties, optically pure plastic scintillants and concentrator of light energy.
Of great importance is the research in the field of creation of special and functional polymers, as well as a wide range of polymeric composition materials (CM), especially, hybrid and modified nanomaterials.
In the field of prospective research for development of new processes of gas chemistry, we will note the development of method of prereforming of associated petroleum gas for production of synthetic gas, which also includes joint fractional gas-phase oxidation of hydrocarbons mixtures, resulting in a considerable reduction of С2-С4 hydrocarbons content with simultaneous increase of methane content. It provides an opportunity of further conversion of the obtained mix into a synthetic gas in the presence of known catalyzers without soot formation and carburizing of catalyzers. Scientific basis of the process of conversion of hydrocarbon gases on the base of membrane technologies and new generations of catalytic systems are being developed. There have been proposed original nanopatterned catalytic systems Pt-Sn on Al2O3 and Cr2O3 + Al2O3, obtained by plasmo-chemical method. In terms of conversion, selectivity and resistance to coke production, the new catalyzers exceed the properties of known contacts. Researchers also studied ways of formation of multilayer membrane-catalytic elements for the synthesis of olefins by way of dehydration of light paraffins. Also, the construction of membrane-catalytic reactor has been proposed.
The processes in question are characterized by high output and quality of obtained products, meet the contemporary requirements of efficient use of energy and resource, they ensure a complex solution of problems of ecological cleanliness and high economic efficiency.
