A method of producing a catalyst for the synthesis of methylmercaptan and dimethyl sulfide
(57) Abstract:Use: petrochemical industry, in particular the production of catalysts for the synthesis of methylmercaptan and dimethylsulfide. The inventive catalyst is prepared by impregnation lumbridge media the pore radius of 100 nm and a specific volume of 0.8 to 0.13 cm3/g with a solution of potassium tungstate. The impregnated carrier is calcined in a preheated oven at 380 - 500oC. the Catalyst contains a 7.5 -10 wt.% the potassium tungstate. table 1. The invention relates to improved methods for producing mercaptan with a high content of dimethyl sulfide and can be used in the production of methylmercaptan, and in the process of production of dimethyl sulfide.Known alumina carrier, structural and mechanical properties which regulate boron compounds and further heat treatment 
However, the resulting lumbardy media does not provide simultaneously high yield of mercaptan and dimethyl sulfide.A method of obtaining methylmercaptan, selected as a prototype, in which to obtain the activated catalyst is used, the oxide aluminia use the sulfides of the metals or salts and oxides of potassium, for example, a carbonate or potassium tungstate in an amount of 10 wt. 
However, the catalyst also does not provide simultaneously high yield of mercaptan and dimethyl sulfide.The aim of the invention is to increase the yield of dimethyl sulphide in the process of obtaining mercaptan using a catalyst containing potassium tungstate.The objective is achieved by the fact that the use of catalyst for the synthesis of mercaptan from methanol and hydrogen sulfide by impregnation lumbridge media the pore radius of 100 nm, a volume of 0.08 to 0.13 cm3/g solution wolframate potassium content in the finished catalyst 7.5 to 10 wt. with subsequent annealing in a preheated oven at 380-500aboutC.As a carrier, it is preferable to use boron aluminum oxide, obtained by the method of thermo-mechanical activation.Thus, the proposed method in contrast to the known is characterized by a number of significant differences in the production technology: the use of media with the pore radius of 100 nm, a volume of 0.8 to 0.13 cm3/g; application of potassium tungstate in the amount of 7.5 to 10 wt. subsequent calcination of the catalyst Les stage of deposition of the active component is immediately stage heat treatment at t 380-500aboutWith, without stages of wilting and drying.The method is as follows.The aluminum oxide containing2ABOUT3the number 2-3,6 wt. and the volume of macropores with r > 100 nm 0.08 to 0.13 cm3/y capacity is sprayed through nozzles aqueous solution of potassium tungstate to the content of potassium tungstate in the finished catalyst 7.5 to 10 wt.The obtained semi-finished product without wilting in the air and drying in a drying Cabinet is placed immediately for 2-4 h in a pre-heated up to t 380-500aboutWith oven.Test the activity of the catalysts in the reaction between hydrogen sulfide and methane to form LCA was performed in a flow-through setup with 380aboutC and a molar ratio of H2S:CH3HE _1,8.Analysis of the initial mixture and the composition of the gas after contact with the catalyst is carried out chromatographically.The distribution of the pore radii were determined by the method of mercury porometry on paramere 2000 company "Sarlo rba" (Italy).P R I m e R 1 (the prototype). To 91 g of aluminum oxide with a specific surface area of 230 m2/g add a solution of potassium tungstate, with a content of 10 wt. in the finished catalyst. The catalyst was dried, calcined. Content is and 1.7 mol
P R I m m e R 2. To 91 g of aluminum oxide containing 3.6% B2ABOUT3and the specific volume of the macropores of 0.08 cm3/y capacity spray impregnating solution containing 8 g of potassium tungstate in 71 ml of water with a speed of 0.3 l/h per 100 g of catalyst.Next, the catalyst mass is placed in an oven, preheated to 380aboutC, and incubated for 4 hThe content of H2WO4in the catalyst 8 wt.The output of methylmercaptan 65 mol%
The yield of dimethyl sulfide 14 mol%
P R I m e R 3. Similar to example 2, only the volume of pores with r > 100 nm is equal to 0.13 cm3/, Content K2WO4in the catalyst 8 wt.P R I m e R 4. Similar to example 2, only the content of potassium tungstate in the finished catalyst is 7.5 wt.P R I m e R 5. Similar to example 2, only the content of the K2WO4in the catalyst is 6 wt.P R I m e R 6. Similar to example 2, only the content of the K2WO4in the finished catalyst 13 wt.P R I m e R 7. Similar to example 2, the temperature of calcination is equal to 330aboutC.P R I m e R 8. Similar to example 2, the temperature of calcination is 500aboutAnd the content of the active components is in the catalyst 8% present stage of wilting on the air 6 h, stage of drying at t 120aboutWith 4 hours.P R I m e R 10. Similar to example 2, the temperature of calcination 600aboutC.P R I m e R 11. Similar to example 2, only the volume of pores with r > 100 nm 0.05 cm3/,P R I m e R 12. Similar to example 2, only the volume of pores with r > 100 nm of 0.15 cm3/,Examples describing the proposed method, shown in the table.Using the presented method of preparation of the catalyst was possible to obtain a high yield of mercaptan (65 mol.) and at the same time dimethyldisulfide (11,5 14 mol.).As can be seen from examples 2,3,4 and 8, the use of boron oxide with aluminum pores radius r > 100 nm, a pore volume of 0.08 to 0.13 cm3/g and the content of potassium tungstate in the finished catalyst 8-10 wt. leads to increase in the yield of dimethyl sulfide.When increasing the volume of pores with r > 100 nm more of 0.13 cm3/g (example 12) loss of strength of the catalyst for reducing the volume of pores with r > 100 nm less than 0.08 cm3/g (example 11) decreases the yield of mercaptan and dimethyl sulfide.The concentration of potassium tungstate in the finished catalyst is 7.5-10 wt.The decrease in the number of K2WO4< 7.5 m WO4> 10 wt. (example 6) decreases the yield of dimethyl sulfide and the goal is not reached.It can be assumed that the decrease in the content of potassium tungstate leads to the release of acidic centers, stimulating the reaction of dimethyl sulfide.The obtained catalyst mass immediately after impregnation placed in a preheated furnace (t 380-500aboutC), resulting in a catalyst, in the presence of the release of dimethyl sulfide equal 11-14 mol% while maintaining a high yield of mercaptan.With increasing temperature of annealing above 500about(Example 10) output dimethyl sulfide falls.If under the same conditions of preparation of the active catalyst additionally carry out the stage of wilting and drying at t 120about(Example 9) output dimethyl sulfide is reduced to 4.5 mol.An increase in the yield of dimethyl sulfide, apparently related to the amount and distribution of the active ingredient by volume of the granules of the catalyst.Thus, using the proposed method provides compared to prototype the advantage of increasing the yield of dimethyl sulfide while maintaining a high yield of mercaptan.
3/g and the impregnation is carried out until the content of potassium tungstate in the finished catalyst 7.5 to 10.0 wt. % followed by annealing in a preheated oven at 380 - 500oC.
FIELD: petrochemical processes and catalysts.
SUBSTANCE: invention relates to supported olefin metathesis catalyst and to a olefin metathesis process using the latter. Catalyst is essentially composed of transition metal or oxide thereof, or a mixture of such metals, or oxides thereof deposited on high-purity silicon dioxide containing less than: 150 ppm magnesium, 900 ppm calcium, 900 ppm sodium, 200 ppm aluminum, and 40 ppm iron. When pure 1-butene comes into interaction with this catalyst under metathesis reaction conditions, reaction proceeds with 2-hexene formation selectivity at least 55 wt %. Use of catalyst according to invention in olefin metathesis process minimizes double bond isomerization reactions.
EFFECT: increased olefin metathesis selectivity regarding specific products.
17 cl, 2 tbl, 2 ex
SUBSTANCE: invention can increase the efficiency of processes of nonoxidising conversion of methane due to increase in activity of W-containing zeolite catalysts. Described is the zeolite catalyst ZSM-5 for process of nonoxidising conversion of methane which has in its composition tungsten in the form of nano-sized powder, thus the content of tungsten in the catalyst is from 4.0 up to 10.0 mass %. Also the method of the preparation of zeolite catalyst for the process of nonoxidising conversion of methane is described, including modification of zeolite by tungsten as a solid, thus tungsten is introduced into zeolite in the form of nano-sized powder of the metal, obtained by the method of electrical explosion of the conductor in the environment of argon, thus the content of tungsten in the obtained catalyst is from 4.0 up to 10.0 mass %. The method of nonoxidising conversion of methane in the presence of zeolite catalyst is described.
EFFECT: obtaining of a catalyst with higher activity during conversion of methane in aromatic hydrocarbons.
3 cl, 1 tbl, 7 ex
SUBSTANCE: description is given of a catalytic composition, containing: a) oxygen compound of an element, chosen from group IVB of the periodic table of elements; b) oxygen compound of an element, chosen from group VIB of the periodic table of elements; c) not less than approximately 1 wt % particles of colloidal silicon dioxide relative to the total mass of the catalyst; d) aluminium compound; and e) group VIII metal. Description is also given of the method of chemical conversion of a hydrocarbon, involving reaction of the hydrocarbon under conditions of the chemical conversion reaction with the given catalytic composition.
EFFECT: increased activity and selectivity of the catalytic composition.
16 cl, 3 tbl, 7 ex
SUBSTANCE: catalyst includes carrier, which contains tungsten oxide or hydroxide of at least one element from grope IVB ("ИЮПАК 4"), first component from at least one element from lanthanide line, yttrium and their mixture, and second component, which contains at least one component of metal from platinum group or their mixture. Also described is method of hydrocarbons transformation by contacting of raw material with solid acid catalyst, described above, with transformed product formation. Described is method of paraffin raw material isomerisation by its contacting with said catalyst at temperature from 25 to 300°C, pressure from 100 kPa to 10 MPa and volumetrical speed of liquid feeding from 0.2 to 15 hour-1 , with further product release, enriched by isoparaffins.
EFFECT: stability in hydrocarbons transformation process, increase of isoparaffins content.
10 cl, 1 tbl, 2 ex, 8 dwg
SUBSTANCE: invention relates to caesium and tungsten-containing oxide catalyst of alkylmercaptane synthesis, method of its production and method of obtaining alkylmercaptanes with its application. Described is catalyst including oxide composition, which corresponds to general formula CsxWOy, in which x represents number from 0.8 to less than 2, and y represents number from 3.4 to less than 4. Described is method of production of catalyst which contains oxide compounds of caesium and tungsten, which lies in the following: a) carriers or substance-carrier, consisting of aluminium oxide is impregnated with water solution containing soluble caesium and tungsten compound with required molar ratio of caesium and tungsten given above, b) obtained impregnated formed carriers or obtained impregnated highly-dispersive aluminium oxide (preliminary prepared catalyst) are subjected to preliminary drying at room temperature, c) if necessary they are subjected to drying at temperature within the range from 100 to 200°C in order to remove residual moisture, d) are subjected to final burning during 2-10 hours at temperature within the range from 300 to 600°C and e) applied catalyst or impregnated highly-dispersive aluminium oxide is obtained, with content of promoter of general composition CsxWOy, where x and y have given above values, in amount from 15 to 45 wt %, preferably from 20 to 36 wt %, after which f) impregnated highly-dispersive aluminium oxide is suspended with addition of known auxiliary substances and applied on core-carrier from inert material or is extruded and pressed. Also described is method of obtaining alkylmercaptane by interaction of alkanols with hydrogen sulphide in presence of catalyst described above.
EFFECT: increase of catalyst activity and selectivity.
14 cl, 2 tbl, 10 ex
SUBSTANCE: invention refers to methylmercaptane synthesis prepared from aluminium oxide, alkali metal wolframate and at least one of ammonium salt containing sulphur or nitrogen with catalyst pH in water suspension 10% being 5.0 - 9.7. The method of methylmercaptanes preparation from methanol and hydrogen sulfide using said catalyst is described also.
EFFECT: enhancing of catalyst activity and selectivity particularly at low hydrogen sulfide/methanol ratios.
6 cl, 2 tbl, 4 ex
SUBSTANCE: invention relates to a catalyst which contains a tungstate of an alkali metal containing at least one halide, where the alkali metal component is selected from a group comprising Cs, Rb or the alkali metal component implies a combination of two bonded alkali metals selected from a group comprising a) potassium and caesium, b) sodium and caesium, c) rubidium and caesium, in ratio not equal to 1:1. Also disclosed is a method of preparing a supported catalyst containing a tungstate of an alkali metal and a method of producing alkylmercaptans.
EFFECT: catalyst has high activity and selectivity which increases output of alkylmercaptans and economical effectiveness of their synthesis process.
28 cl, 9 ex, 1 tbl
SUBSTANCE: catalyst for synthesis of alkyl mercaptans has a support or contains support material and catalytically active tungstate which contains at least one chemically bonded alkali metal and tungsten having formula AxWOy, in which A denotes at least one alkali metal (provided that caesium can be present only combined with another element from the group of alkali metals), x denotes a number ranging from 0.9 to less than 2, and y denotes a number ranging from 3.4 to less than 4. The method of preparing a catalyst which contains tungstate of an alkali metal involves a) impregnation of a supports or support material with an aqueous solution containing dissolved compounds of alkali metal(s) and tungsten in the required molar ratio between the alkali metal(s) and tungsten, b) the obtained impregnated moulded supports or the obtained impregnated fine-grained support material (catalyst prepared beforehand) are subjected to preliminary drying at room temperature, c) if necessary, drying is carried out at temperature ranging from 100 to 200°C in order to remove residual moisture, d) final calcination is done for 2-10 hours at temperature ranging from 300 to 600°C and e) a supported catalyst or impregnated fine-grained support material containing a promoter with general formula AxWOy is obtained, where A denotes at least one alkali metal (provided that caesium can be present only combined with another element from the group of alkali metals), x is a number from 0.9 to less than 2, and y is a number from 3.4 to less than 4, in amount ranging from 8 to 45 wt %, preferably from 15 to 36 wt %, after which e) the impregnated fine-grained support material is suspended by adding known additives and then deposited on core-support made from inert material or extruded and moulded.
EFFECT: obtaining a catalyst which has high activity and selectivity at low molar ratio of hydrogen sulphide to methanol.
25 cl, 8 ex, 1 tbl
SUBSTANCE: invention relates to heterogeneous catalytic conversion of organic compounds, specifically to catalytic conversion of a mixture of aliphatic alcohols to a mixture of alkane-olefin hydrocarbons, particularly C5-C8 hydrocarbons. Described is catalyst for synthesis of alkane-olefin hydrocarbons based on γ-aluminium oxide, distinguished by that, the catalyst contains tungsten oxide and rhenium oxide with the following ratio of components, in wt %: tungsten oxide 1.2-6.7; rhenium oxide 0-1.3; γ-aluminium oxide - the rest. Described also is a method for synthesis of alkane-olefin hydrocarbons with an even or combined even and odd number of carbon atoms through cross-coupling reaction of ethanol or its mixture with aliphatic alcohols in the presence of the said catalyst.
EFFECT: described catalyst enables to increase output of C5-C8 olefin-alkane fractions to 45% and reduce output of gaseous C1-C2 products to 30-35% with 85-95% conversion of initial alcohols.
5 cl, 5 tbl, 3 dwg, 9 ex
SUBSTANCE: invention relates to an improved method for synthesis of an ester through reaction of 1-olefin with a monobasic carboxylic acid and water in vapour phase in the presence of a heteropolyacid catalyst on silica gel, in which the silica gel support is in from of granules treated with water vapour at temperature between 100 and 300°C for a period of time between 0.1 to 200 hours, before or simultaneously with application of the heteropolyacid onto the support. The invention also relates to a heteropolyacid catalyst deposited on silica gel and to a method of preparing the catalyst, where the support is obtained by treating silica gel granules with water vapour at temperature between 100 and 300°C for a period of time between 0.1 and 200 hours, before or simultaneously with application of the heteropolyacid onto the support.
EFFECT: use of the said catalyst in the ester synthesis method through reaction of 1-olefin with a monobasic carboxylic acid and water in vapour phase enables to reduce content of methyl ethyl ketone in products.
43 cl, 1 ex