The Project aim. Development of polyoxide modified by rare earth elements of a new type of catalysts on carriers and cleans technology to produce of synthesis gas from methane and carbon dioxide, the study of the structural properties of optimal catalysts to identify the physico-chemical basis of their actions in the oxidative conversion is planned to carry out in the course of the project. Manufacture of the enlarged laboratory reactor and installation. Preparation of experimental batch of optimal catalyst for testing in long-term conditions on the enlarged set in the optimum process conditions. Issuing recommendations on the implementation.
Current status. Currently in the process of exploratory studies of the catalytic oxidative conversion of methane in the presence of carbon dioxide has been shown the possibility of using previously developed a multi-component NiCuNdMo/20% Al2O3-HZSM-5 catalyst supported on granular carrier for the steam-oxygen conversion of methane. Maximum yields of synthesis gas (H2 - 49 vol.%, CO - 50 vol.%) and the highest conversion of the initial reagents (XCH4 - 92.6% and XCO2 - 92.3%) are achieved on this catalyst in preliminary experiments at T = 850oC. Analysis of the literature allows to conclude that the processes and catalysts for the selective production of synthesis gas in a single step from greenhouse gases (CH4 + CO2) studied and developed not enough yet. The process of carbon dioxide reforming of methane has not yet been widely adopted in the industry as the low activity and thermal stability, as well as the carbonization of catalyst are a major problem. Major efforts in this area focused on developing of highly efficient and thermally stable catalysts.
The project’ influence on progress in this area. As a result of completion of the planned experiment we will obtain a sum of products, consisting of synthesis gas, and possibly methanol, dimethyl ether and other valuable industrially important products. Synthesis gas may be used not only for the Fischer-Tropsch synthesis, but also as a reducing gas for metallurgical processes. Production of methanol from synthesis gas in parallel with the other components of the oxidative dehydrogenation of methane is important for the oil industry. The use of dimethyl ether for a diesel engine, and as an additive in mixtures with gasoline sharply increases the efficiency of the combustion and cleanliness of waste gas.
The participants’ expertise. Employees participating in the project have extensive experience in research in the field of oxidative catalysis, studying the mechanism of action and control the properties of effective new nanosized catalysts and sorbents for selective processing of natural gas into organic synthesis products and fuel compositions, as well as neutralization of waste gas of industrial enterprises and vehicles. CPCMA is accredited in the accreditation system of the Republic of Kazakhstan on conformity to requirements the "General requirements for the competence of testing and calibration laboratories"(Appendix 1: Accreditation certificate number KZ.I.02.0817 from 01/06/2010 valid until 01/06/2015).
Organization (JSC "Kaustik"), involved into the implementation of project has experience in conducting of experimental studies, the development of working schemes, manufacture of metal constructions and construction of catalytic apparatus. Accredited testing central chemical laboratory operates at the enterprise that allows testing of all types of products directly on the company (Appendix 2: Accreditation certificate number KZ.I.14.1055 from 09/12/2010 valid until 09/12/2015).
Expected results and their application. Thermostable polyoxide new type catalysts on carriers modified with rare earth elements, and environmentally friendly technology for producing of synthesis gas from methane and carbon dioxide will be developed as a result of the project. Morphology of optimal catalyst will be studied by complex of physical and chemical methods, the factors determining the activity and thermal stability of catalysts in continuous operation will be identified and rational ways the selection of catalysts for producing of synthesis gas from methane and carbon dioxide will be offered. Optimum compositions of the synthesis gas used in the Fischer-Tropsch synthesis will also be determined. Experimental batch of catalyst will be produced and catalytic technology will be tested in a pilot plant. Recommendations for implementation will be issued. Obtained results will have a practical value for oil and gas sector, petrochemical synthesis, metallurgical industry, etc. Studies on the development of catalysts and processes for the production of synthesis gas from methane involving carbon dioxide, which is produced by burning of fuel, have economic and environmental interest, taking into account the lack of industrial processes for the processing of large stocks of alkanes in Kazakhstan. Assumed that the project "Development of catalyst and technology of utilization of greenhouse gases - methane and carbon dioxide," can be introduced in one of boiler rooms of the thermal power plant (TPP) in Kazakhstan, where natural gas - methane is used as fuel and carbon dioxide is produced as a result of its burning.
Meeting the ISTC goals and objectives. The project quite corresponds to ISTC purposes as the experts possessing skills in the field of the weapon of mass defeat are occupied, and the project has exclusively peace orientation. During project realisation the reorientation and conversion of JSC Кaustik will be carried out with attraction of weapon experts to manufacture of peace production of the consumer goods. The workplaces for research activity in the peace purposes in the field of environment protection will be created for experts-armourers. Performance of researches in the field of oil and gas technologies will promote integration of the Kazakhstan scientists with the International scientific community by information representation on project at the international conferences and symposiums. Creation of competitive technologies which can be realised in the conditions of market economy will promote utilization of greenhouse gases to give commercially important products and public health care, and also an animal and flora preservation.
Scope of activities. Following basic works will be executed within the framework of the project:
- development of composition and method of preparation of supported polyoxide catalysts modified with rare earth metals for the process of oxidative conversion of methane in the presence of carbon dioxide to produce synthesis gas;
- selection of optimal process parameters of the catalytic conversion of greenhouse gases into synthesis gas;
- determination of physical and chemical characteristics of the developed catalysts and their relationship to the catalytic activity;
- manufacture of enlarged laboratory reactor and setting;
- preparation and testing of the developed optimal catalyst on stability in the enlarged installation at optimized process conditions of process.
Role of Foreign Collaborators/Partners. Prof. Robert Farrauto (Columbia University, Earth and Environmental Engineering Department, New York, USA), Prof. Raymond J. Gorte (University of Pennsylvania, School of Engineering and Applied Science, Department of Chemical and Biomolecular Engineering, USA), Prof. Jacek Koziel (Iowa State University of Science and Technology, Department of Agricultural and Biosystems Engineering, IA, USA), Associate Professor Hideki Kurokawa (Saitama University, Graduate School of Science & Engineering, Saitama, Japan), Prof. Dmitry Yu. Murzin (Head of the Laboratory of Industrial Chemistry and Reaction Engineering, Abo Akademi University, Turku/Abo, Finland), Prof. Slavcho Rakovsky (Institute of Catalysis, Bulgarian Academy of Sciences, Bulgaria) are the collaborators of the project. The role of collaborators in the project consists in information interchange during project realisation, consultations, joint publications, participation in working seminars, an exchange of experience, granting of responses on performance of the program of the project, registration of joint patents.
Technical approach and methodology. Catalysts on carriers will be prepareв by precipitation methods of transition metals oxides by impregnation of carrier on moisture capacity with the use of dispersing agents to obtain nanophase particles of active phase. The principles of designing of the known constructions developed earlier in laboratory will be used at designing of catalytic reactor and installation. Test model of reactor will be made on test base of JSC "Kaustik" with participation of experts-armourers. Attraction of experts of the CPCMA is possible. Laboratory installation on methane oxidation will be collected on the basis of the available equipment, and also with use of the devices got on means from the project. Development of technology and manufacturing of an experimental batch of the catalyst is planned on test base of the CPCMA. During of project realization the technical problems connected with preparation of catalysts on granulated carriers with drawing of an active phase will be solved. Methodology of the given project is transition from laboratory samples to test models which will be tested on the integrated installation. Research of catalysts by modern physical and chemical methods will be carried out at CPCMA and on the available equipment and nano-laboratory of collective use of the al-Farabi Kazakh National University.
