The method of producing catalyst for the oligomerization of lower olefins
(57) Abstract:The invention relates to the field of petrochemical industry, namely the production of catalysts for the oligomerization of lower olefins. The method consists in thermal pyrolysis of petroleum or natural gas at a temperature 310-960oC, space velocity of the raw material 800-1200 h-1within 0.3-10 h in the presence of Nickel chloride with subsequent screening by fractionating the resulting catalyst mass at a molecular sieve fraction 45-400 μm. Technical result: method solves the technical problem of exception use in the process of preparation of the catalyst chloride diethylamine. 3 table. The invention relates to the field of petrochemical industry, namely the production of catalysts for the oligomerization of lower olefins. The resulting oligomers can be used as modifying additives for motor fuels, for the synthesis of surfactants, etc.A known method of producing a catalyst for the oligomerization of lower olefins (Patent Germany 1937232, CL 01 J, publ. 1973), which consists in the interaction of bis-(triisopropylphosphine)-likelihood with poly(4-vinylpyridine method is the swelling of the polymer base, what makes a supply of feedstock to the catalytic centers and the removal from them of the reaction products. Do not exclude the possibility of contamination of the oligomer decomposition products of the polymer base, which under the action of the catalytic complex may react with oligomere or with the original monomer.The closest technical solution to the claimed invention is a method for preparing the oligomerization catalyst, in particular of dimerization (Patent US 3465056, 02.09.1969 g), consisting in the use of Nickel chloride, reacting with chloride diethylaluminium deposited on a carbon basis. As the carbon base, in a decision taken by activated charcoal.The disadvantage of this method is the use of alyuminiiorganicheskikh connection, which belongs to the category of highly toxic substances.The present invention solves the technical problem of exception use in the process of preparation of the catalyst chloride diethylamine.The above technical result is achieved by the known method of preparing the oligomerization catalyst, consisting in the use of Nickel chloride, reacting with chloride of diet the structure carry out thermo catalytic pyrolysis of petroleum or natural gas in terms of its contact with Nickel chloride at a temperature 310-960oC, space velocity of the raw material 800-1200 h1within 0.3-10 h followed by screening by fractionating the resulting catalyst mass at a molecular sieve fraction 45-400 μm, which is experienced as a catalyst for the oligomerization of lower olefins with 38-153oWith time and mixing 1-5 PMThe hallmark of the invention is that the Nickel chloride contact in the conditions of the pyrolysis of petroleum or natural gas, resulting in a gain chloride Nickel deposited on the carbon fiber, which eliminates the use in the process of preparation of the catalyst chloride diethylamine.Example. In a quartz reactor with a volume of 1 l load 1 g of Nickel chloride, heated to 450oWith, then carry out a thermal pyrolysis by filing in the chloride layer associated petroleum gas made by field (fractional composition shown in table. 1) with a bulk velocity of 1000 h1. After 2 h, the process is stopped. Formed on the surface chloride carbon deposits have a fibrous structure, while ensuring uniform distribution of catalyst throughout the structure of carbon fiber (physico-chemical s 20oWith and subjected to fractionation by molecular sieves, selecting the fraction 45-400 microns.In a stainless steel autoclave with a capacity of 0.5 l is placed 0.12 g selected fractions 45-400 μm catalyst mass, blow dried inert gas. Then, the autoclave is pressurized, cooled in carbon dioxide and filled with 100 g of propylene. Incubated 3 h at 80oWith in a rotating system, which is cooled, distilled entered in the reaction of propylene (3 g) and obtain 97 g of propylene oligomers that share ratifikaciey and analyzed chromatographically. You get to 67.9 g (70%) of dimers of propylene, of 12.6 g (13%) of trimers, 10.7 g (11%) tetramers and 5.8 g (6%) more than high-boiling components. The latter are of a colorless transparent liquid, different from the lighter oligomers of lower mobility and higher viscosity. The conversion of propylene is 97%. The catalyst activity was assessed by the conversion of the original monomer.Examples of preparation of the catalyst are given in table. 3.The catalyst according to the invention has a high activity, as the conversion of monomer in the oligomerization of lower olefins is 96-99%.This invention can find Sib allows to increase the efficiency of the process through the use of more accessible and non-deficient hydrocarbons (petroleum or natural gas), as well as to improve environmental safety, excluded from the formulation of the preparation of the catalyst phase catalytic activation framework toxic alyuminiiorganicheskikh connection. The method of producing catalyst for the oligomerization of lower olefins, carbon-based with the use of Nickel chloride, characterized in that the receiving carry out thermo catalytic pyrolysis of petroleum or natural gas in terms of its contact with Nickel chloride at a temperature 310-960oC, space velocity of the raw material 800-1200 h-1within 0.3-10 h followed by screening by fractionating the resulting catalyst mass at a molecular sieve fraction 45-400 μm.
FIELD: composition and structure of composite metal semiconductor meso-porous materials; titanium-dioxide-based catalyst for photo-chemical reactions.
SUBSTANCE: proposed catalyst is meso-porous titanium-dioxide-based material containing crystalline phase of anatase in the amount no less than 30 mass-% and nickel in the amount no less than 2 mass-%; material has porous structure at average diameter of pores from 2 to 16 nm and specific surface no less than 70 m2/g; as catalyst of photo-chemical reaction of liberation of hydrogen from aqua-alcohol mixtures, it ensures quantum reaction yield from 0.09 to 0.13. Method of production of such catalyst includes introduction of precursor - titanium tetraalkoxyde and template of organic nature, holding reagent mixture till final molding of three-dimensional structure from it at successive stages of forming sol, then gel, separation of reaction product and treatment of this product till removal of template; process is carried out in aqua-alcohol solvent containing no more than 7 mass-% of water; at least one of ligands is introduced into solvent as template; ligand is selected from group of macro-cyclic compounds containing no less than four atoms of oxygen and/or from complexes of said macro-cyclic compounds with ions of metals selected from alkaline or alkaline-earth metals or F-metals containing lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium; mixture is stirred before forming of sol maintaining its temperature not above 35°C till final molding of three-dimensional structure from reagent mixture; mixture is held in open reservoir at the same temperature at free access of water vapor; after removal of template from three-dimensional structure, mixture is first treated with nickel salt solution during period of time sufficient for withdrawal of nickel ions from solution by pores of structure, after which is it kept in hydrogen-containing medium during period of time sufficient for reduction of nickel ions in pores of structure to metallic nickel.
EFFECT: enhanced sorption and photo-catalytic parameters; reproducibility of catalyst properties.
7 cl, 68 ex