Method for the production of methylmercaptan, a method of producing a catalyst for the production of methylmercaptan and a method of producing hydrogen sulfide for the production of methylmercaptan

 

(57) Abstract:

The invention relates to the production of odorants for natural gas, in particular waste-free way to obtain mercaptan, as well as to a method for producing a catalyst, providing a higher degree of interaction between methyl alcohol and hydrogen sulfide and the use of such a method of producing hydrogen sulfide, which provides waste reduction production in General. Methyl mercaptan is produced by transmission of a binary mixture of vapors of methyl alcohol and hydrogen sulfide at atmospheric pressure through successively installed along a mixture of tubular reactors with catalyst, the return of the unreacted components of the mixture in the head process of adding the necessary quantity of methyl alcohol and hydrogen sulfide and the separation of the components of the production of the gas mixture by condensation. As the catalyst used, the oxides of molybdenum or tungsten, the process is carried out at a temperature of 390 - 430oC and flow rate of the mixture in the reactor at the level of 100 - 1000 h-1using hydrogen sulphide, obtained by the reaction of dilute acid and metal sulfide, and the condensation is carried out stepwise emitting creating what adenium 8 30oC and the resulting mercaptan by passing the remaining mixture at a temperature of 0 - (-5)oC through the solution, neutral hydrogen sulphide salts, such as calcium chloride with a concentration of 0.5 to 6 wt.%. The number of reactors installed in series is at least two. The method of producing the catalyst is in the preparation of a solution containing compounds of tungsten or molybdenum, impregnation obtained by the solution of the porous media and its subsequent drying and firing. For solution preparation with a concentration of from 0.1 wt. % to busy using the tungstate or ammonium molybdate in solution is injected water-soluble polymer in an amount of 0.1 - 30 wt.% from the mass of water taken, porous media prior to treatment is subjected to molding and sintering, after impregnation carry out the drying at 400 - 450oC for 1 to 4 hours and then in a stream of inert gas, for example nitrogen, at 300 - 450oC for 1 to 4 hours as porous media using a clay - ultra lightweight or diatomite. As the water-soluble polymer used methylcellulose, polyvinylpyrrolidone or polyvinyl alcohol. A method of producing hydrogen sulfide for the production of methylmercaptan includes the decomposition of sulphide of barium is barium restore natural gas in countercurrent pouring thermochemical reactor at 950 - 1050oC for 50 - 60 minutes, and the resulting barium sulfide is again directed to the interaction. The technical result consists in increasing the degree of conversion of the initial reagents, in a secure process in environmental protection because of the almost complete elimination of emissions of gases containing harmful substances, solid and liquid waste. 3 S. and 6 C.p. f-crystals, 1 Il.

The invention relates to the synthesis of organic compounds, in particular the obtaining of odorants for natural gas, used as fuel in heat and power engineering, transport and other industries.

Methods for producing mercaptans or thiols is widely known in organic chemistry (see Chemical encyclopedia.- M: Great Russian encyclopedia, 1995, I. 4, p. 573). In particular, methods are used, based on the use of reactions leading to the substitution of hydroxyl groups in alcohols on tigraphy. So, methylmercaptan synthesized by the interaction of a solution of potassium hydrosulfide (obtained by saturation of the solution of potassium hydroxide with hydrogen sulfide) neutralized with sodium hydroxide, one stripped off and filtered from sulphate crystals with a mixture of fuming sulfuric acid and the receiver, a cooled mixture of salt and snow to -15oC (see Rapoport, F. M., Elias A. A. Laboratory methods of obtaining pure gases. - M.: Goskomizdat, 1963, c. 414-419). As impurities have some amount of hydrogen sulfide and metilsulfate. However, the product yield in the reaction of methanol is low and amounts to 10-15%. The disadvantage of this method is the presence of side products in the form of sulfate salts. In addition, incomplete may be condensation methylmercaptan, because at the same temperature it has a relatively high vapor pressure.

The method of obtaining pure mercaptan with high yields (about 90%) is as follows. Methylisothiazoline and dimethylsulfate dissolve in water after evaporation and addition of alcohol crystallized sulphate salt, the decomposition of which by heating with an alkaline solution to get the actual mercaptan (see Houben I. Methods of organic chemistry.- M: ONTI, 1935, T. 3, vol. 3, c. 494). As by-products stands out, as in the previous case, the sodium sulfate, and the solid dicyandiamide. Dimethylsulfate for this reaction can be obtained by reaction of chlorosulfonic acid and methyl spirtovozy products and higher cost of reagents, preventing the use of the method on a large scale. Additionally, the compounds have high toxicity.

Also known is a method of obtaining methylmercaptan, including direct synthesis of methylmercaptan from a gaseous mixture containing vapors of methyl alcohol and hydrogen, at a pressure of from 5 to 15 bar and a temperature in the range of 300-500oC in the presence of a catalyst based on aluminum oxide. From the production of a mixture of the mercaptan allocate absorption and distillation methods. The source gas mixture contains an excess of hydrogen sulfide in a molar ratio of hydrogen sulfide to methanol 1,1: 3. Unreacted reagents are in circulation by adding the necessary quantity of hydrogen sulfide and methyl alcohol for the formation of the mixture in the required amount with the original structure (see EP 0850922 A1, C 07 C 319/08, 01.07.1998). One of the examples of the above process, when the molar ratio of hydrogen sulfide to methanol at 1.8 the relative yield of alcohol is about 75% (by sulfide - about 40%). The main disadvantage of this method consists in the application of high pressure during a mandatory requirement for production, >/P>Closest to the proposed method is the direct synthesis of methylmercaptan of binary mixture of equivalent quantities of vapors of methyl alcohol and hydrogen sulfide is carried out at atmospheric pressure by passing the mixture over a catalyst (pumice covered 1/3 of thorium nitrate and heated first to 270oC, and then to 400oC) at 380oC (see Houben I. Methods of organic chemistry. - M. : lecture notes, 1935, T. 3, vol. 3, S. 494). At higher temperatures the product, according to the author of the monograph, is decomposed to hydrogen sulfide and the corresponding alkene (unsaturated hydrocarbon). After the implementation of catalytic reactions remain unspent reagents: hydrogen sulfide and methyl alcohol, which pollute the environment. To prevent this we need to catch that reduces the economic efficiency of the method. Another disadvantage inherent in the known methods of synthesis of methylmercaptan, when as one of the reactants is hydrogen, is getting a variety of waste, for example in the form of solutions of salts of organic compounds. The output of the product under these conditions the process is not more than 41%.

Known for the way the floor is Rapido porous media, for example pumice, a solution of thorium nitrate and thermal decomposition of this salt by stepwise heating of the first to 270oC, and then to 400oC (see Houben I. Methods of organic chemistry.- M: ONTI, 1935, T. 3, vol. 3, c. 494). Actually the catalytic action has formed the thorium oxide (ThO2), which is reportedly the most effective for the process. However, in the this connection uses thorium have natural radioactivity, which is a disadvantage of the method.

Closest to the proposed invention is a method of producing a catalyst for direct synthesis of methylmercaptan from a mixture of vapors of methyl alcohol and hydrogen sulfide, comprising impregnating a porous support such as alumina with a specific surface area of 350 m2/g aqueous solutions of compounds of tungsten and potassium followed by heat treatment (see and.with. EN 2120822 C1, 6 B 01 J 23/30, 27.10.98. Bull. N 30). The main disadvantage of this method is to obtain a catalyst in which the actual catalytic effect has received the oxides of tungsten (VI) in amorphous form, is insufficient for large-scale production activity, which is not ensured a high degree in the tion on the interaction of hydrogen and sulfur at a certain temperature (Nekrasov, B. C. Fundamentals of General chemistry, 1 so. - M. : Chemistry, 1965, S. 310). The interaction process can be described by the following reaction:

H2+ S = H2S + 5 kcal.

The complexity of carrying out such a process has not resulted in its technical use.

Closest to the proposed invention is a method of producing hydrogen sulfide, based on the action of dilute acids on sulfides of metals, such as sulfur iron (Nekrasov B. C. Fundamentals of General chemistry, so-1.- M.: Chemistry, 1965, S. 310)

FeS+2HCl=FeCl2+H2S.

The disadvantages of this method is the inability of the organization cyclic process and the high cost of hydrochloric acid.

The overall technical objective of the present invention is the creation of Autonomous (not primarily tied to the production of hydrogen sulfide) simple waste-free method of producing mercaptan, ensuring full use of the reagents and the selection of the product from the reaction mixture. At the same time solved the problem of obtaining a catalyst, providing a higher degree of interaction between methyl alcohol and hydrogen sulfide without the use of radioactive reagents, and the implementation of such a method of obtaining selenium Autonomous production of methylmercaptan requires only a supply nidificate sulfuric acid and methyl alcohol.

Main technical results of the invention consist in increasing the yield of the main product and the degree of conversion of the initial reagents in the safe conduct of the process of catalysis, environmental protection due to the almost complete elimination of emissions of gases containing harmful substances, solid and liquid waste.

These technical results are achieved due to the fact that in the method of production of methylmercaptan, including the transmission of a binary mixture of vapors of methyl alcohol and hydrogen sulfide at atmospheric pressure through successively installed along a mixture of tubular reactors with catalyst, the return of the unreacted components of the mixture in the head process of adding the necessary quantity of methyl alcohol and hydrogen sulfide and the separation of the components of the production of the gas mixture by condensation, as the catalyst used, the oxides of molybdenum or tungsten, the process is carried out at a temperature of 390-430oC and flow rate of the mixture in the reactor at the level of 100-1000 h-1using hydrogen sulphide, obtained by the reaction of dilute acid and metal sulfide, and the condensation is carried out stepwise with a selection of images of what ladanian to 8-30oC and the resulting mercaptan by passing the remaining mixture at a temperature of 0- (-5)oC through the solution, neutral hydrogen sulphide salts, such as calcium chloride with a concentration of 0.5 to 6 wt.%. The number of reactors installed in series is at least two, mostly 2-6. The original binary mixture is prepared by passing hydrogen sulfide through methyl alcohol, and the content of methyl alcohol in the mixture regulate its temperature. One of the options for the allocation of water, methyl alcohol and mercaptan is carried out after each reactor, the remaining hydrogen sulfide is passed through methyl alcohol, and the resulting mixture is sent to the next reactor, and in the mixture fed to each reactor, support equimolar composition of the reagents. According to another variant of the original mixture contains two to five-fold excess of methyl alcohol against equimolar amount, the allocation of water is carried out after each reactor, and the allocation of methyl alcohol and mercaptan - at the outlet of the last reactor.

In the method of producing a catalyst for the production of mercaptan from a binary mixture of vapors of methyl alcohol and hydrogen sulfide, enabling ristoro media and its subsequent drying and firing, for solution preparation with a concentration of from 0.1 wt.% to rich use tungstate or ammonium molybdate in solution is injected water-soluble polymer in an amount of 0.1-30 wt.% from the mass of water taken, porous media prior to treatment is subjected to molding and sintering, after impregnation carry out drying at a temperature of 50-120oC and calcination in air at a temperature of 400-450oC for 1-4 h and then in a stream of inert gas, for example nitrogen, at a temperature of 300-450oC for 1-4 hours as porous media using a clay - ultra lightweight or diatomite. As the water-soluble polymer used methylcellulose, polyvinylpyrrolidone or polyvinyl alcohol.

In the method of producing hydrogen sulfide for the production of methylmercaptan by decomposition of metal sulfide acid as acid using sulfuric acid, and the metal sulfide - sulfide barium piece-shaped form with a particle size fraction 5-20 mm, formed by the interaction of barium sulfate restore natural gas in countercurrent pouring thermochemical reactor at a temperature of 950-1050oC for 50-60 min, and the resulting barium sulfide is again directed to the interaction.

Servodata and vapors of methyl alcohol through the catalyst, obtained by impregnating a porous support with an aqueous solution of compounds of tungsten or molybdenum, followed by drying and firing, as well as the condensation of the resulting product when cooled. In addition it has the following differences. As a carrier of catalysts used material, which is pre-set the desired configuration and size by molding and sintering, such as clay - ultra lightweight, Aerosil, etc. For preparation of catalysts as salt solutions using solutions with a concentration of from 0.1 wt.% until saturated, and salt take not giving after heat treatment, the impurities in the catalyst, such as molybdate or ammonium tungstate. Solutions for impregnation of carriers include, in addition, water-soluble polymer in an amount of 0.1-30 wt.% from the mass of water taken, after impregnation of the media is subjected to drying at 50-120oC to remove moisture. The firing in air at 400-450oC for 1-4 h and then blowing an inert gas such as nitrogen, at 300-450oC to restore the oxide of the transition metal with getting at least 3% lower oxides of tungsten or molybdenum and the acquisition of a catalyst intense blue or violet color within 1-4 hours

the Alla, for example, barium, with particle size fraction 5-20 mm reduced to sulfide in natural gas in countercurrent pouring thermochemical reactor at a temperature of 950-1050oC and the total time spent in the specified reactor 50-60 minutes Next, the resulting sulfide is treated with sulfuric acid with hydrogen sulphide, and the resulting sulfate is again sent for recovery. It is necessary, from our point of view, to make the following remark. There is a method of recovery of barium sulfate natural gas in fluidized bed furnaces (see, for example, Posin M. E. Technology of mineral salts, part 1, "Chemistry" publishing house, Leningrad branch, 1970, S. 434). High-temperature process in a fluidized bed is extremely complex and has a very low degree (32-36%) reductant use (natural gas). In the case of the present invention is greatly simplified instrumentation with the increasing use of natural gas to 50-60%.

The reaction stoichiometric mixture used in the catalytic synthesis, prepare, passing gaseous hydrogen sulfide through methyl alcohol or mixing with his pairs, adjusting the content of the latter in the mixture by changing the temperature of methyl sleep the torus at a temperature reactors 350-430oC with a bulk velocity of 100-1000 h-1. The number of series-connected reactors from 2 to 6, after each of them spend condensation released in the reaction water cooling up to 70-90oC, and then methyl alcohol cooled to 8-30oC and condensation of mercaptan - by passing the remaining part of the mixture at a temperature of 0-(-5)oC in a solution of salt, not interacting with methylmercaptan and hydrogen sulfide, such as calcium chloride, in a concentration of 0.5-6 wt.%. The remaining hydrogen sulfide after passing through the methyl alcohol is sent to the next reactor. Another option in the reaction mixture using an excess of methyl alcohol with respect to the stoichiometric 2 to 5 times. The condensation of methyl alcohol is carried out after the passing of the last reactor and the operation of the condensation water. Condensed methyl alcohol sent for reuse in the reaction by filing in the vessel, through which pass the hydrogen sulfide. Remaining after completion of all reactors, the hydrogen sulfide is also sent at the beginning of the cycle of synthesis, mixing it with fresh hydrogen sulfide coming from processing of sulphide alkaline earth metal with sulfuric acid.

The use of saturated salt solutions, not giving during the heat treatment, impurities, gives the possibility of obtaining catalysts with maximum saturation of the carrier surface oxides of transition metals with simultaneous decrease of the particle size of the crystallized during drying salts, which increases the specific surface area of catalysts. Salt concentrations less than 0.1 wt.%, do not provide a sufficient amount of catalyst impregnation media.

Additional introduction to the solutions used for impregnation of carriers of water-soluble polymers, for example polyvinyl alcohol, provides for the drying and firing the impregnated carriers are even more significant increase in specific surface area due to the fact that the polymer, linking ions containing transition metals, prevents crystallization of the salt forms, leading to amorphization. In addition polymer-containing solutions have a higher cover and film-forming ability, it is better moisten the surface of the media, increasing the uniformity katsetos for preparation of a solution of water, not provided with the positive effect of increased surface area and improved film formation. On the other hand, greater than 30% of their concentration, lead to an excessive increase in the quantity released during the roasting gases, preventing further notable positive effect.

The temperature of drying of the workpieces is selected based on the fact that at lower temperatures the process of solvent removal becomes too long, and when higher is the boiling't retired yet solvent, which leads to the discontinuity of the catalytic coating and the partial destruction of the media.

The lower limit of the firing temperature of the catalysts chosen so that it provided a complete decomposition of salts, synthesis of transition metal oxide, the fading remnants of the polymeric portion of the composition. The upper limit is limited by the fact that at higher temperatures the oxide catalyst undergoes recrystallization associated with reduced specific surface area, and occur undesirable interaction between the coating and the media, changing the chemical nature of the catalyst, which reduces the activity of the latter. The firing time is selected isprocess, and longer economically feasible, leading to additional energy consumption for firing, because these processes are practically implemented in sufficient to ensure a positive effect. Additional calcination of the catalyst in the inert gas allows to obtain partially restored the shape of the oxide of the transition metal (i.e., lower oxides of tungsten or molybdenum, corresponding to the chemical formula WO3-x, MoO3-xwhere x = 0,05-0,5) that is necessary for the synthesis of methylmercaptan catalytic activity. The interval of firing temperature in this case is selected based on the fact that lower temperatures do not lead to the restoration of sufficient oxide, and at higher temperatures it undergoes recrystallization with a decrease in specific surface area. A sign describing the implementation of a partial recovery, is the acquisition of a catalyst intense blue or purple coloration, therefore, the heat treatment process is carried out before the acquisition of the specified color within 1-4 hours

Temperature 350-430oC, which was in the reactor the catalyst was selected taking into account the fact that at lower tampereentie was possible to obtain a sufficiently high yield of mercaptan. Higher temperatures resulted in lower product yield due to its thermal decomposition.

The volumetric rate of passing the reaction mixture through the catalyst 100-1000 h-1was taken because at speeds greater than 1000 h-1reaction time to adequately and reduced product yield. Less than 100 h-1that speed was slowed synthesis and were impractical because of the increased consumption of catalysts.

The particle size fraction 5-20 mm source of sulfates of alkaline earth metals used for the reason that a larger fraction do not have time to react in a thermochemical reactor, and smaller require special grinding with an additional investment of time and energy, in addition, allocate a significant amount of dust. The advantages of the method is that used for obtaining hydrogen sulfide sulfates low cost are the wastes of other industries that can solve the problem of disposal and improvement of ecological situation. Temperature thermochemical processing and time selected in the range 950-1050oC and 50-60 min, respectively, because at lower values of these parameters are not achieved dottorini so, in order to avoid additional consumption of energy and time than necessary to obtain a positive effect.

The selection of the ratio of components in the reaction mixture was based on the fact that in the case of stoichiometric amounts of 1:1 is observed, the maximum yield of the product at each stage of the synthesis. Advantages of using excessive quantities of methyl alcohol is the possibility of implementing technological schemes where there are no operations condensation of methanol and methylmercaptan after each of the reactors. The excess methanol is in the range of 2-5 times, because at higher amount is reduced relative yield in the reaction and spent more energy for vaporization and condensation. Smaller surpluses lead to the fact that after the first reactor, the composition of the mixture approaches the stoichiometric and the reaction slows down.

Temperature intervals of condensation of water is selected based on the fact that at higher temperatures the condensation is not complete because of the high saturated vapor pressure. The lower limit is limited by the need to prevent the operation of the condensation of significant quantities of methyl alcohol. Similar about the Sabbath. Condensation of the target product should be carried out in the temperature range 0-(-5)oC, because at higher temperatures the condensation takes place not fully, at lower - there is a need for additional cooling costs receivers. The use of salt solutions to absorb mercaptan justified by the fact that during condensation in a conventional receiver, it is mixed with unspent hydrogen sulfide, which increases the volatility of the obtained product and reduces its extraction from the reaction mixture. Introduction saline as another phase available mixture reduces the volatility of the product, increasing its output at the stage of separation of the components and does not require cooling to lower temperatures. The concentration of the salt solutions is chosen so that the absorption was, on the one hand, effectively (at concentrations above 6 wt.% the amount of condensation of mercaptan per unit volume of the solution falls), on the other hand solutions with less 0.5% concentration cannot be cooled to the required temperature without freezing.

The drawing shows a schematic diagram of receipt of methylmercaptan one of the options. The recovery of barium sulfate in stage 1 takes place when filing in the apparatus itself barium sulfate and prirodnogo methyl alcohol evaporates at stage 3. The reaction mixture enters the reactor at the stage of receipt of methylmercaptan 4. After the process of methylmercaptan 4 a mixture of gases passed through the stage of condensation of water 5, the condensation of methyl alcohol 6 and condensation of methylmercaptan 7. After the first stage in a gas mixture of fresh hydrogen sulfide, and at the second stage again repeat stages 3, 4, 5, 6 and 7. The ignition of natural gas is performed on stage 8, using hot gas after combustion to heat the natural gas before recovery of barium sulfate, heating the sulfide and equipment. The condensed methyl mercaptan is the final product, the condensation of methyl alcohol use again in the process, the condensed water is used for dilution of sulphuric acid.

Example 1.

We've taken the carriers of catalysts from clay - ultra lightweight, molded and sintered in such a way that were obtained cylindrical billet with a diameter of 20 mm and a thickness of 10 mm. Carriers were impregnated by immersing them in a saturated solution of ammonium molybdate containing 0.1 wt.% methylcellulose, and then subjected to drying to remove moisture at a temperature of 50oC, then fired at a temperature of 400oC for 4 h in the Kim way catalysts, containing 3.2% of the lower oxides of molybdenum, were placed in two sequentially installed tubular reactor and was applied to them after they have been heated to 350oC, the reaction mixture obtained by passing hydrogen sulfide through methyl alcohol containing equimolar quantities of hydrogen sulfide and methyl alcohol. While hydrogen sulfide was prepared as follows. The original barium sulfate with a particle size of 5 mm was restored in counterflow pouring thermochemical reactor natural gas at 950oC and the total time spent in 60 minutes Then the resulting barium sulfide was treated for separation of hydrogen sulfide sulfuric acid, and the resulting barium sulfate was sent again to restore. After passing the reaction mixture of the first reactor was cooled to 90oC, which was accompanied by condensation released during the reaction water, then there was further cooled to 30oC with the release of unreacted methyl alcohol. Condensation of methylmercaptan was carried out by passing the remaining part of the reaction mixture through an aqueous solution of calcium chloride containing 6 wt.% this salt at a temperature of -5oC. the Remaining hydrogen sulfide was again barbotirovany through methyl alcohol the promotional mix after the first reactor. The volumetric rate of passage of the mixture through the reactor was 100 h-1. Remaining after the second reactor of unreacted hydrogen sulfide is sent at the beginning of the cycle of synthesis, mixing with fresh portions of this gas. Condensed methyl alcohol used in the reaction by filing it in the tank through which blew the hydrogen sulfide. Thus, there was obtained 12.2 g of methylmercaptan at the rate of 8.6 g of methyl alcohol. The use of reagents during operation of synthesis in cyclic mode was 98%.

Example 2.

We've taken the carriers of catalysts from diatomite, molded and sintered so that there were obtained spherical workpieces with a diameter of 2 mm. Carriers were impregnated by immersing them in a 0.1% solution of ammonium tungstate containing 30 wt.% polyvinylpyrrolidone, and then subjected to drying to remove moisture at a temperature of 120oC, then fired at a temperature of 450oC for 1 h in air and within 4 hours prior to the acquisition of catalyst violet color at 300oC in a stream of nitrogen. Thus obtained catalysts containing 4.1% of the lower oxides of tungsten, was placed in a tubular reactor and was applied to them after their heat 4 times more methyl alcohol, than the stoichiometric quantity. Hydrogen sulfide was prepared as follows. The original barium sulfate with a particle size of 20 mm was restored in counterflow pouring thermochemical reactor natural gas at 1050oC and the total time of stay there 50 minutes Then the resulting barium sulfide was treated for separation of hydrogen sulfide sulfuric acid, and the resulting barium sulfate was sent again to restore. After passing the reaction mixture of the first reactor was cooled to 70oC, which is accompanied by condensation released during the reaction water. After that, the reaction mixture is sent to the next stage of the synthesis, the total number was 6. After passing the reaction mixture of the last reactor and condensing water conducted further cooling to 8oC with the release of unreacted methyl alcohol. Condensation of methylmercaptan was carried out by passing the remaining part of the reaction mixture through an aqueous solution of calcium chloride containing 0.5 wt.% this salt at a temperature of 0oC. the space velocity of the mixture passing through the reactor was 1000 h-1. Remaining after completion of all reactor unreacted hydrogen sulfide was sent in on the reaction by filing it in the tank, through which blew the hydrogen sulfide. Thus, there was obtained 16.7 g of methylmercaptan at a flow rate of 11.2 g of methyl alcohol.

The use of the proposed technical solution, which is a group connected by a single concept of the invention provides the following technical and economic advantages:

- the autonomy of the production of mercaptan from hydrogen sulfide and methyl alcohol, is associated mainly with obtaining hydrogen sulfide directly in production of the main product,

- waste reduction process of obtaining hydrogen sulfide and methylmercaptan,

exclusion of emissions of gaseous, liquid and solid substances, polluting the environment,

- high degree of interaction vapors of methyl alcohol and hydrogen sulfide, provided the proposed catalyst and technology,

an exception upon receipt of the expensive catalyst components,

the simplicity of the proposed method,

- a cyclic process, ensuring full use of the original substances.

1. Method for the production of methylmercaptan, including the transmission of a binary mixture of vapors of methyl alcohol and hydrogen sulfide at atmospheric pressure through posledovatel mixture in the head process of adding the necessary quantity of methyl alcohol and hydrogen sulfide and the separation of the components of the production of the gas mixture by condensation, characterized in that the catalyst used, the oxides of molybdenum or tungsten, the process is carried out at a temperature of 390 - 430oC and flow rate of the mixture in the reactor at the level of 100 - 1000 h-1using hydrogen sulphide, obtained by the reaction of dilute acid and metal sulfide, and the condensation is carried out stepwise emitting formed by the reaction of water cooling the gas mixture to 70 - 90oC, unreacted methyl alcohol cooled to 8 - 30oC and the resulting mercaptan by passing the remaining mixture at a temperature of 0 - (-5)oC through the solution, neutral hydrogen sulphide salts, such as calcium chloride with a concentration of 0.5 to 6 wt.%.

2. The method according to p. 1, characterized in that the number of reactors installed in series is at least two, mostly 2 - 6.

3. The method according to PP. 1 and 2, characterized in that the source of the binary mixture is prepared by passing hydrogen sulfide through methyl alcohol, and the content of methyl alcohol in the mixture regulate its temperature.

4. The method according to PP.1 to 3, characterized in that the allocation of water, methyl alcohol and mercaptan spend pic to the next reactor, moreover, in the mixture fed to each reactor, support equimolar composition of the reactants.

5. The method according to PP. 1 to 3, characterized in that the starting mixture contains two to five-fold excess of methyl alcohol against equimolar amount, the allocation of water is carried out after each reactor, and the allocation of methyl alcohol and mercaptan - at the outlet of the last reactor.

6. A method of producing a catalyst for the production of mercaptan from a binary mixture of vapors of methyl alcohol and hydrogen sulfide, comprising preparing a solution containing compounds of tungsten or molybdenum, impregnation obtained by the solution of the porous media and its subsequent drying and firing, characterized in that for the preparation of a solution with a concentration of from 0.1 wt. % to busy using the tungstate or ammonium molybdate in solution is injected water-soluble polymer in an amount of 0.1 - 30 wt.% from the mass of water taken, porous media prior to treatment is subjected to molding and sintering, after impregnation carry out the drying at 50 - 120oC and calcination in air at 400 - 450oC for 1 to 4 hours and then in a stream of inert gas such as nitrogen at 300 - 450oC for 1 to 4 h

7. The method according to p. 6, characterized in that characterized in that as a water-soluble polymer used methylcellulose, polyvinylpyrrolidone or polyvinyl alcohol.

9. A method of producing hydrogen sulfide for the production of methylmercaptan by p. 1 by decomposition of metal sulfide acid, wherein the acid using sulfuric acid, and the metal sulfide - sulfide barium piece-shaped form with a particle size fractions 5 to 20 mm, the formed barium sulfate restore natural gas in countercurrent pouring thermochemical reactor at 950 - 1050oC for 50 - 60 minutes, and the resulting barium sulfide is again directed to the decomposition.

 

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FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalyst of olefin monomers trimerisation. Described is catalytic composition for olefin monomers trimerisation, which contains a) source of chrome, molybdenum or tungsten; b) ligand if general formula (I), in which X stands for bivalent organic group, selected from substituted or non-substituted alkylene groups, in case of substituted groups, substituents represent hydrocarbon groups; R1 and R3 represent cycloaromatic groups, which do not contain polar substituents in none of orto-positions; R2 and R4 are independently selected from obligatory substituted cycloaromatic groups, each of R2 and R4 having polar substituent in at least one orto-position; and c) cocatalyst. Also described is method of olefin monomers trimerisation, including interaction of at least one olefin monomer in conditions of trimerisation reaction with said above catalytic composition.

EFFECT: selective obtaining 1-hexagen from ethylene, reducing level of formation of by-products, especially C10.

10 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to catalytic system and to the method of reduction of nitrogen oxides emissions using the said system. The described catalytic system for NOx reduction contains: the catalyst containing the metal oxide substrate, catalytic metal oxide which is gallium oxide or silver oxide or both of them and initiating metal chosen from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth and their mixtures, gas flow containing the organic reducing agent and sulfur-containing substance. The described catalytic system for NOx reduction contains: the catalyst consisting of (i) the metal oxide substrate, containing aluminium oxide, (ii) catalytic metal oxide which is gallium oxide or silver oxide or both of them in quantity 1-31 mole %; and (iii) initiating metal or their combination selected from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth, indium and wolfram, silver and cobalt, indium and molybdenum, indium and silver, bismuth and silver, bismuth and indium and molybdenum and indium in quantity 1-31 mole %, gas flow containing (A) water in quantity 1-15 mole %; (B) gaseous oxygen in quantity 1-15 mole %; and (C) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations; and sulfur oxide; where at the specified organic reducing agent and NOx are present in approximate molar ratio carbon to NOx from 0.5:1 to 24:1. The described method of NOx reducing includes the stages of gaseous mixture containing NOx, organic reducing agent and sulfur-containing substance inflow and of said gaseous mixture contact with specified catalyst. The described method of NOx reduction includes: inflow of gaseous mixture containing (A) NOx, (B) water in quantity 1-15 mole %; (C) oxygen in approximate quantity 1-15 mole %; (D) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations and (E) sulfur oxide; and contact of said gaseous mixture with catalyst described above and containing the specified components in the defined molar ratio.

EFFECT: improved action of the catalyst.

35 cl, 10 tbl, 84 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for pyrazinamide synthesis during reaction of oxidative ammonolysis methylpyrazine. Alkyl-substituted pyrazines and their derivatives have high biological activity, which enables their wide use as medicinal agents for different purposes. Described is a catalyst for synthesis of oxidative ammonolysis methylpyrazine containing vanadium pentoxide and titanium dioxide and modifying additives from a group of elements of oxidative nature such as tungsten W or molybden Mo, with the following content of components, wt %: V2O5 10-29, TiO2 70-79, WoO3 or MoO3 1-10. Also described is a method of producing pyrazinamide through oxidative ammonolysis methylpyrazine in the presence the catalyst described above.

EFFECT: proposed catalysts enable production of pyrazinamide in a single step and increase total output of pyrazinamide and pyrazinonitrile.

2 cl, 8 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst system and a method of reducing nitrogen oxide emissions. The described catalyst system for reducing NOx contains: a catalyst having a support which contains at least one compound selected from a group consisting of aluminium oxide, titanium dioxide, zirconium dioxide, cerium oxide, silicon carbide and mixtures thereof, a catalytic metal oxide containing at least one of gallium oxide or silver oxide and at least one activating metal selected from a group consisting of silver, cobalt, molybdenum, tungsten, indium or mixtures thereof; and a gas stream containing oxygen ranging from approximately 1 mol % to approximately 12 mol % and an organic reducing agent selected from a group consisting of alcohol, carbonate or combinations thereof, where the said organic reducing agent and the said NOx are present in molar ratio carbon: NOx ranging from approximately 0.5:1 to approximately 24:1. A catalyst system for reducing NOx which contains the following is described: a catalyst consisting of (i) metal oxide support which contains aluminium oxide, (ii) at least one of the following oxides: gallium oxide or silver oxide, present in amount ranging from approximately 5 mol % to approximately 31 mol %; and (iii) an activating metal or a combination of activating metals, present in amount ranging from approximately 1 mol % to approximately 22 mol % and selected from a group consisting of silver, cobalt, molybdenum, tungsten, indium and molybdenum, indium and cobalt, and indium and tungsten; and a gas stream containing (A) water in range from approximately 1 mol % to approximately 12 mol %; (B) oxygen in the range from approximately 1 mol % to approximately 15 mol %; and (C) an organic reducing agent containing oxygen and selected from a group consisting of methanol, ethanol, butyl alcohol, propyl alcohol, dimethyl carbonate or combinations thereof; where the said organic reducing agent and NOx are present in molar ratio carbon: NOx ranging from approximately 0.5:1 to 24:1. Also described are methods of reducing NOx which involve the following steps: providing a gas mixture and bringing the said gas mixture into contact with above described catalysts for reducing NOx (versions).

EFFECT: reduced ill effects of air contamination caused by by-products of incomplete high-temperature combustion of organic substances.

21 cl, 34 ex, 4 tbl

FIELD: oil and gas industry.

SUBSTANCE: invention refers to catalysts intended to open naphthene rings. There described is catalyst for opening naphthene rings, which includes platinum component, ruthenic component and modifying component, and they are all dispersed on a substrate from high-melting non-organic oxide, and is characterised by the fact that at least 50% of platinum and ruthenic components is present in the form of particles, where on particle surface there is concentration of ruthenium, which is higher than that in the centre of particles. There also described is method for obtaining acyclic paraffins from cyclic ones, which involves contact of flow of raw material containing cyclic paraffins with the catalyst containing platinum component, ruthenic component and modifying component, and they are all dispersed on a substrate from high-melting non-organic oxide, in conditions of opening the ring in order to prevent at least some part of cyclic paraffins to acyclic paraffins; at that, catalyst is characterised by the fact that at least 50% of platinum and ruthenic components is in the form of particles, where on particle surface there is concentration of ruthenium, which is higher than that in the centre of particles.

EFFECT: increased synergism of Pt/Ru catalysts.

10 cl, 8 ex, 6 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention describes a method of obtaining middle distillates from a paraffin fraction obtained through Fishcer-Tropsch synthesis using a hydrocracking/hydroisomerisation catalyst which contains at least one hydrogenating-dehydrogenating element selected from a group comprising group VIB and group VIII periodic table elements, 0.01-6% phosphorus as a dopant and a non-zeolite substrate based on aluminium silicate, wherein said aluminium silicate has the following characteristics: 5-95 wt % silicon oxide content, less than 0.03 wt % sodium, total pore volume of 0.45-1.2 ml/g measured using mercury porosimetry,porosity is such that ii) volume of mesopores with diametre of 40-150 Ǻ and average pore diametre of 80-140 Ǻ is 30-80% of the total pore volume measured with mercury porosimetry, ii) volume of macropores with diametre of over 500 Ǻ is 20-70% of the total pore volume measured with mercury porosimetry, specific BET surface area is 100-550 m2/g, the X-ray pattern contains at least main characteristic spectra of at least one of transition aluminium oxide included in the group of alpha, rho, chi, eta, gamma, kappa, theta and delta aluminium oxides.

EFFECT: improved method.

20 cl, 2 tbl, 4 dwg, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates to catalyst of hydraulic treatment and/or conversion of heavy hydrocarbon beds. Proposed catalyst comprises aluminium oxide-based carrier, at least, one catalytic metal or compound of catalytic metal of group VIB and/or VIII with porous structure consisting of multiple, contact agglomerates, each formed by multiple needle-like plates. Note here that plates of every agglomerate are oriented radially relative to each other and to agglomerate center. Note that aforesaid agglomerate features irregular and non-spherical shape, exists in the form of fragments produced by crushing aluminium oxide balls and is obtained in the following stages: a) granulation of the powder of active aluminium oxide that feature poorly crystallised and/or amorphous structure to produce ball-shaped agglomerates; b) curing in humid atmosphere at 60°C to 100°C. Then, balls are dried; c) screening to recover fractions of aforesaid balls; d) crushing of aforesaid fraction; e) calcination of, at least, a part of said fraction at 250°C to 900°C; f) impregnation by acid and hydrothermal treatment at 80°C to 250°C; g) drying followed by calcination at 500°C to 1100°C. Invention covers also the method of hydraulic treatment and/or conversion of heavy hydrocarbons containing metals incorporating above described catalyst.

EFFECT: improved process performances in hydraulic conversion and/or treatment of heavy hydrocarbons beds.

28 cl, 8 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: composition is based on zirconium oxide, silicon oxide and one oxide of another element M, selected from titanium, aluminium, tungsten, molybdenum, cerium, iron, tin, zinc and manganese, with the following weight ratio of these different elements: silicon oxide: 5-30%; oxide of element M: 1-20%, and up to 100% zirconium oxide, wherein the composition has acidity defined in experiments using methylbutanol equal to at least 90%. Said composition can be obtained using a method in which a liquid medium is mixed with a zirconium compound, a silicon compound, a compound of element M and a basic compound, as a result of which a precipitate forms; the precipitate then matures in the liquid medium, separated and then calcined.

EFFECT: composition is effective in treating exhaust gases of diesel engines.

23 cl, 11 tbl, 16 ex

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