Method for continuous receipt of methylmercaptan

 

(57) Abstract:

The invention relates to a method of continuous receipt of methylmercaptan through catalytic interaction of methanol with hydrogen sulfide in the vapor phase at a temperature of 300-500°C. In the preparation of the initial gas mixture required for evaporation of the methanol energy is provided partially through the use of contained in the effluent from the reactor a gaseous product of heat. Reaction heat is used for heating using an external visonaries source gas mixture to the reaction temperature. By optimizing the process of making the initial gas mixture and the best use of the heat of reaction increases the efficiency of the whole process regarding investment costs and ongoing energy costs. 5 C.p. f-crystals, 2 Il.

The invention relates to a method of continuous receipt of mercaptan by reacting contained in the source gas mixture of methanol and hydrogen sulfide in the vapor phase at the reaction temperature from 300 to 500oC and under a working pressure of from 5 to 15 bar on the layer of catalyst based on aluminum oxide with subsequent absorption and distillation separation of mercaptan mixture from hatoum inert gases and sewage and replacement of the spent methanol and hydrogen sulfide.

The mercaptan is an industrially important intermediate product for the synthesis of methionine, as well as for obtaining dimethyl sulfoxide and dimethyl sulfone. Currently, it is produced mainly from methanol and hydrogen sulfide by the reaction on the catalyst is aluminum oxide. Synthesis of methylmercaptan usually occurs in the gas phase at a temperature of from 300 to 500oC and a pressure of from 1 to 25 bar. To improve the activity and selectivity of the catalyst, the latter is usually covered with potassium tungstate as a promoter. The interaction of hydrogen sulfide and methanol education methylmercaptan is exothermic, in which KMOL unreacted methanol is allocated 28500 kJ of energy.

The mixture of gaseous reaction products contains along with formed mercaptan and water unreacted educt methanol and hydrogen as by-products of dimethyl sulphide and dimethyl ether, as well as small amounts of polysulfides. In addition, a mixture of gaseous reaction products contains inert under the conditions of this reaction gaseous dioxide and monoxide, nitrogen and hydrogen.

The resulting mercaptan distinguish from x at a temperature of from 10 to 140oC. at the same time as other threads products are formed, the excess hydrogen sulfide, methanol, inert gases and waste water. As drilling fluid is preferably used methanol.

Excess hydrogen sulfide return in the form of a so-called recirculation gas in the pressure reactor. The recirculation gas along with hydrogen sulfide also contains methanol, methyl mercaptan, dimethyl sulfide, and other components of the mixture of gaseous reaction products. The share of these components in the recirculation gas depends on the quality of the separation process. Unspent methanol also return in the original gas mixture. Similarly, the recirculation gas is returned into the process methanol contains other components. Consumed quantities of hydrogen sulfide and methanol supply by the supply of fresh media.

The whole process of getting the mercaptan can be divided into two phases. The first stage covers the preparation of the initial gas mixture and its transformation into methyl mercaptan. The second stage involves the separation of a mixture of gaseous reaction products from the receipt of methylmercaptan and return unspent methanol and hydrogen sulfide, as well as the utilization of Stocznia get methylmercaptan.

The nature of the initial preparation of the gas mixture, it is heated to the reaction temperature and the subsequent cooling of the mixture of gaseous products with the objective of condensation and separation of methylmercaptan have a significant impact on the economy of the whole process. For compressors require large electric power, and more power for heating and cooling.

In the patent DE 1768826 shows only a small information regarding this first stage of the process. From the presented scheme can be seen that the recirculation gas together with fresh gaseous hydrogen sulphide is heated in the heat exchanger hot mixture of gaseous products. At the same time the mixture of gaseous products of the reaction is cooled. Necessary for the reaction of methanol after heating of hydrogen sulfide in the heat exchanger is added to the sulfide shortly before feeding into the reactor with the formation of the source gas mixture. To do this, separated from the mixture of gaseous products wash methanol is withdrawn from the wash recirculation flow. Selected from the wash recirculation flow quantity replenished with fresh methanol.

According to the patent FR 2477538 for poluchelovekom sulfide admixed returned from the process gas recirculation, containing hydrogen sulfide, dimethyl sulfide, methanol and small amounts of mercaptan, with the formation of the source gas mixture. The temperature of the source gas mixture is increased to 510oC in the oven preheating. Before entering the first of the series-connected reactors, which can reach ten, to the source gas mixture is admixed wash recycle stream containing methanol and dimethyl sulfide. The resulting temperature at the inlet of the reactor is reduced to 450oC. Before the second and subsequent reactors is injected into the gas stream of additional quantities of methanol partly in liquid and partly in the form of gas. However due to the required heat of evaporation of the methanol can be absorbed all the heat or of heat, which is released by the reaction.

In the patent DE-PS 1134368 described the use of a tubular reactor for the production of methylmercaptan. The tubular reactor consists of a cylindrical tank in which parallel arranged tubes with catalyst. Tube top and bottom welded tube sheets as tubular heat exchangers. The annular space is filled with heat-conducting fluid. Each tube the removal of the gas mixture flows through the reactor from the bottom up.

The catalyst consists of activated alumina in the form of beads with a particle size of from 8 to 14 mesh. In the lower section of the tubes, the catalyst is preferably diluted with particles of inert substances, such as silicic acid or molten aluminum oxide, and an inert substance accounts for about 75% of the particles in the lower third of the tube. From this height, the amount of inert substances is reduced to the upper part of the tubes so that the tubes in the upper part contain only pure catalyst. The gradual dilution of the catalyst in the flow direction provides a more uniform heat, allowing easier temperature control.

In the patent DE-PS 1134368 as a heat transfer liquid used eutectic mixture of phenyl ether and diphenyl. The coolant evaporates due to heat of reaction and again condensed in the tank for the coolant is returned to the reactor. According to DE-PS 1134368 the source gas mixture is heated by the heat exchange with hot gaseous mixture of reaction products and hot vapors of the cooling liquid.

The present invention was based on the task to develop a way of gaining the use of the heat of reaction increases the efficiency of the whole process regarding investment costs and ongoing energy costs.

This problem is solved by using the method according to the restrictive part of the formula of the invention, which differs in that the source gas mixture is obtained by:

a) compression of fresh gaseous hydrogen sulfide to an intermediate pressure with the addition of liquid methanol,

b) blending in a circulating gaseous hydrogen sulfide to the fresh gas and compressing the resulting mixture to a working pressure

C) introducing an additional amount of methanol vapor in the compressed gas mixture with the formation of the source gas mixture with a molar ratio between hydrogen sulfide and methanol from 1.1 to 3,

g) heating the source gas mixture to a preliminary temperature in the range from 150 to 200oC,

d) further heating the source gas mixture to the reaction temperature by heat exchange with eye-catching on the layer of catalyst heat of reaction.

According to the invention the fresh gaseous hydrogen sulfide in the first stage is first compressed from the normal pressure to an intermediate pressure. However, gaseous hydrogen sulfide add liquid methanol before or during the compression process by spraying or injection. Under the action of the released compression of warmth methanol part of the>C. After compression of the gas stream at a temperature that occurs after the first stage of compression, saturated with methanol.

Separated from the mixture of gaseous reaction products and returned to the process of gaseous hydrogen sulfide, below designated as recycle gas, is compressed together with the pre-compressed fresh gas in the second stage from the intermediate pressure to the operating pressure. By limiting the temperature of the first stage compression gas temperature after the second stage of compression is increased only up to the maximum 140oC.

In the injection of methanol in the first stage compression part of the energy of compression is used for evaporation of methanol while simultaneously reducing the temperature in the first stage of compression. This prevents investment costs usually requires a smart fridge, as well as ongoing costs for the cooling water. Further savings due to the fact that the part required for the reaction of methanol evaporates under the influence of the liberated heat of compression.

After the second stage of compression in the source gas mixture is injected additional amount of methanol vapor to obtain a molar ratio between ceravolo is the conversion of hydrogen sulfide and methanol to methyl mercaptan. However, a large excess of hydrogen sulfide also means that you need to recycle large quantity. Therefore, to limit the necessary energy molar ratio should not exceed 3. At values below 1.1, on the contrary, the conversion of the mercaptan even when using highly active and selective catalysts unsatisfactory. Therefore, preferably the molar ratio of from 1.5 to 2.0.

Evaporated in the first stage of compression, the amount of methanol depends on the selected intermediate pressure and the selected molar ratio. The more the molar ratio, the greater the amount of hydrogen sulfide relative to methanol should be compressed and the greater the amount of methanol can be evaporated. Preferably choose an intermediate pressure, which corresponds to half the operating pressure. In this case, it may be evaporated, for example, at a molar ratio of 1.8 and an intermediate pressure of 6 bar in the first stage, about 25% of the total required for the reaction of methanol.

The temperature thus obtained the source gas mixture is increased to a preliminary temperature in the range of 150-200oC by supplying external heat from visonaries catalyst heat of reaction and is passed through a bed of the catalyst for the conversion of hydrogen sulfide and methanol to methyl mercaptan.

In one preferred embodiment of the invention, the catalytic interaction is carried out in a tubular reactor tube which is filled in the flow direction of a first layer of granular inert material, then a layer of granular catalyst, and released on the layer of catalyst reaction heat is transferred circulating between the tubes teploperenosa environment to a located upstream layer of inert material for heating the source gas mixture to the reaction temperature. For this teploperenosu medium pumped through the annulus of the reactor countercurrent to the source gas mixture is transported thereby released on the layer of catalyst reaction heat to the layer of inert material. As teploperenosa environment is acceptable, for example, molten salt. The length of the layer of inert material and a catalyst layer, and the preliminary temperature (temperature at the inlet of the reactor) can be very simply agreed with each other so that the source gas mixture after passing through a layer of inert material was heated to the reaction temperature of 300-500oC.

This mode of operation of the reactor has many advantages. For example, Vesnin may respectively have a simple design. In contrast, in the patent FR 2477538 source gas mixture before entry into the reactor must be heated to 510oC. this requires expensive hasingredient with a large heating capacity. He must be made of corrosion resistant materials, because, as you know, hydrogen sulphide at temperatures above 500oC has a strong corrosive effect.

The presence of internal heat transfer in the reactor allows you to abandon appropriate measures to remove heat of reaction. Necessary to control the reactor temperature of the heating and cooling device for circulating teploperenosa environment can be made correspondingly small. In contrast, according to patent DE 1134368 all the heat of reaction calculated from the refrigerant to the outside and passed the initial gas mixture in a separate heat exchanger.

In another of the preferred embodiment of the invention required for evaporation of the methanol energy is extracted in the heat exchanger from a mixture of gaseous reaction products after the release of the pressure reactor. When this gaseous mixture of products is cooled to between 100 and 150oC. Contained in a mixture of gaseous pre 137oC and a pressure of 10 bar is only necessary for use in the process of quantity of methanol. Thanks to the binding evaporation of methanol to heat of reaction required for the reaction molar ratio between hydrogen sulfide and methanol is set mostly automatically.

Divided into two stages of compression of the source gas to the operating pressure preferably is carried out in a two-stage compressor, and the gas mixture is compressed in the first stage to an intermediate pressure, and the second stage to the operating pressure. For this purpose the most suitable two-stage screw compressors. These compressors are compact and reliable. Methanol can be injected directly into the first stage of compression. In addition, it was found expedient to inject methanol in excess, i.e., to apply a greater amount of methanol compared to those that can be vaporized by the heat of compression. Redundant, not evaporated methanol appears at the output of the first stage of the compressor and returns to its entrance. This part of the circulating liquid methanol washes first stage compressor and removes from it the large deposits of sulphur. Washed with methanol particles are separated on the filter. The ratio of the b mass ratio of 2:1.

Below the invention is explained more with the help of drawings on which is shown:

in Fig. 1 - flow chart of the first stage of the process of obtaining mercaptan,

in Fig. 2 is a detailed image of the tubular reactor with a layer of granular inert material and catalyst and circulation teploperenosa environment.

In Fig. 1 shows a process diagram of the first stage of the process of obtaining methylmercaptan, which includes the process of preparation of the original gas mixture, the interaction in the reactor and cooling the mixture of gaseous products.

Interaction in a tubular reactor 5 is the catalyst of granulated aluminum oxide, coated with 25 wt.% of caesium tungstate. The grain size of the granules is about 3 mm. This catalyst is described in detail in the unpublished patent application DE Germany 19639584, example 2. The catalyst is capable of conversion into methyl mercaptan source gas mixture with a molar ratio between hydrogen sulfide and methanol from 1.5:1 to 2.0:1 at an operating pressure of 10 bar, the reaction temperature from 340 to 370oC and at an average hourly rate of gas supply (SCPG) from 800 to 1200 h-1with the conversion of methanol and selectivity, respectively, more than the stage I of a two-stage screw compressor 1 with the simultaneous injection of liquid methanol to the intermediate pressure 6 bar. Due to the heat of compression of a portion of the methanol is evaporated and thereby limits the temperature after the first stage of compression is about 65oC. evaporated under the action of the heat of compression methanol recycle through the buffer tank 2, and from it, using used for this purpose filter removes particles that were washed out of the compressor. The flow rate of the evaporated methanol at a molar ratio from 1.5:1 to 2.0:1 corresponds to approximately 20-30% of methanol required for the reaction, and is compensated flow 21 of methanol from the other buffer capacity 3.

In a compressed to an intermediate pressure fresh gas is injected stream 22 recirculation of gaseous hydrogen sulfide. Then this gas mixture is compressed in the second stage II of the screw compressor to 11 bar. This is the final pressure of the screw compressor is slightly greater than the actual operating pressure in the reactor, allowing you to compensate for pressure losses in the piping. In the selection of the heat of compression, the temperature of the gas mixture rises to approximately 100-110oC.

For a given molar ratio between hydrogen sulfide and methanol in the compressed gas stream 23 add a pair 24 of methanol. Methanol vapor are t the I gas mixture 25 is heated in hasanaginica 4 to the temperature at the inlet of the reactor (temperature) 150-200oC. With this temperature of the source gas mixture into the reactor 5 and is heated in the heat exchange with eye-catching on the layer of catalyst warm reaction to the reaction temperature.

A mixture of 26 gaseous products released from the reactor with the reaction temperature. It contains heat is used in the heat exchanger 6 for evaporation of the methanol. The mixture of gaseous products of the reaction is cooled to approximately 150oC and fed as stream 27 to the second process stage of the process. The separation of the mixture of gaseous reaction products on its components is carried out in the second process stage of the process of obtaining mercaptan. Separation may be effected in various known ways. The most appropriate use of the method of separating a mixture of gaseous products, which are described in the parallel patent application Russia 97121987.

The important point is that separated in the second process stage of the process the gaseous hydrogen sulfide is returned to the process in the form of recirculated gas 22. The same applies to separate from the mixture of gaseous reaction products are not fully consumed during the interaction in the reactor OCA returned as stream 28 in the buffer tank 3.

Consumed in the process of obtaining the amount of methanol is filled with fresh methanol, which is in the form of a stream 29 is supplied to the buffer vessel 3.

From the buffer tank 3 are selected stream 30 for washing with methanol in the second stage of the process and the flow 31 of methanol for catalytic reactions. Thread 31 of methanol is divided into two partial flow 21 and 32, and the thread 21 is evaporated in the first stage of the compressor, and the flow 32 is transferred into the vapor phase during the heat exchange with hot gaseous mixture of reaction products.

In Fig. 2 shows a preferred embodiment of the reactor according to p. 2. In the reactor 5 between the two tube sheets 9 and 10 parallel to each other are welded tube 11 with the catalyst. The source gas mixture 25 is supplied in tubes with catalyst distribution through space 13. Tube 11 with the catalyst filled in the direction of flow of the source gas mixture first inert layer 7 made of ceramic Raschig rings, and then a layer 8 of granular catalyst. After leaving the tubes of the reacted gas mixture through a gathering space 14 is fed as stream 26 gaseous reaction products for further processing.

Intermediate cavity 12 between Trou the olo 150oC) as teploperenosa environment 33. Teploperenosa medium is fed through the reactor in counter-current to the source gas mixture. For this teploperenosa environment derived from the reaction vessel under the tube sheet 9 and again at the external contour above the tube sheet 10 in the intermediate cavity 12. Position 15 marked the circulation pump is required to circulate the coolant.

Thanks recirculation teploperenosa environment heat of reaction released in the catalyst layer 8, is transmitted to the source gas mixture on the area of the layer 7 of inert material. To regulate the temperature of the reactor is provided a heat exchanger 16 for heating and cooling teploperenosa environment.

In Fig. 2 shows the preferred orientation of the tubular reactor. The tubes are arranged vertically, and the source gas mixture passes through the reactor from top to bottom. The lower openings of the tubes are supplied sootvetstvujushej grating serving as a support for the layer of granular catalyst. However, the reactor may have any other orientation.

The temperature of the source gas mixture at the inlet to the reactor is C. steady state of about 170oC. For heating the source Gaea length of the tube with the catalyst.

Coming out of the reactor thread 26 of the gaseous products at a molar ratio of 1.8 (hydrogen/methanol) has the following typical composition, wt.%:

The mercaptan - 39

Dimethyl sulphide - 1,6

Dimethyl - 2,7

Inert gases (H2, CO, CO2N2) - 2,5

Water - 15

The sulfide - 34

Methanol - 5

In the flowsheet of Fig. 1 shows the components required for implementing the method according to the invention. Not shown, additional components, which are required only as an auxiliary means for starting phase of the way. These include probortunity evaporator methanol, which until then, until the start of the catalytic reaction vaporizes the required amount of methanol, because there is no gaseous reaction product. During this starting phase is also used and the heat exchanger 16 for heating the reactor. If necessary, the scheme may provide for additional electric heating.

Proposed according to the invention the method differs optimal use of eye-catching in the process of energy flows. These energy flows are primarily used directly on the stage of the method, the required methanol evaporates resulting from the use of heat, released during the compression of the fresh gaseous hydrogen sulfide. To this end, the methanol is injected directly into the compressor, thereby making unnecessary additional cooling of the compressor.

The source gas mixture is heated to the reaction temperature in the reactor by using eye-catching on the layer of catalyst heat of reaction. External hasingredient needed only for heating the source gas mixture to a relatively low temperature at the inlet of the reactor and may therefore be correspondingly simple design.

1. Method for continuous receipt of mercaptan by reacting contained in the source gas mixture of methanol and hydrogen sulfide in the vapor phase at the reaction temperature from 300 to 500oC and under a working pressure of from 5 to 15 bar on the layer of catalyst based on aluminum oxide with subsequent absorption and distillation separation of mercaptan from a mixture of gaseous reaction products and return to the process unspent methanol and hydrogen sulfide, as well as the removal of inert gases and sewage and replacement of consumed quantities of methanol and hydrogen sulfide, characterized in that the source gas mixture is obtained by: (a) Eshiwani circulating gaseous hydrogen sulfide to the fresh gas and compressing the resulting mixture to a working pressure C) introducing an additional amount of methanol vapor in the compressed gas mixture with the formation of the source gas mixture with a molar ratio between hydrogen sulfide and methanol from 1.1 to 3, g) heating the source gas mixture to a preliminary temperature in the range from 150 to 200oC, d) further heating the source gas mixture to the reaction temperature by heat exchange with eye-catching on the layer of catalyst heat of reaction and (e) interaction of methanol and hydrogen sulfide on the catalyst layer with the formation of mercaptan.

2. The method according to p. 1, characterized in that the interaction is carried out in a tubular reactor tube which is filled in the flow direction of a first layer of granular inert material, then a layer of granular catalyst, and released on the layer of catalyst reaction heat is transferred circulating between the tubes teploperenosa environment to a located upstream layer of inert material for heating the source gas mixture to the reaction temperature.

3. The method according to p. 1 or 2, characterized in that the amount of heat necessary for the evaporation of additional quantities of methanol are selected from a mixture of gaseous reaction products from the completion of the fact, the source gas mixture is compressed in a two-stage compressor, and the gas mixture is compressed in a first stage to an intermediate pressure and a second stage to the working pressure.

5. The method according to p. 4, characterized in that as a compressor used two-stage screw compressor, and the liquid methanol is injected directly into the first stage of the compressor.

6. The method according to p. 5, characterized in that the liquid methanol inject in excess of, and not evaporated portion of the recycle.

 

Same patents:

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

The invention relates to catalysts for the synthesis of methylmercaptan used in the production of methionine, agricultural chemicals and other chemical compounds

FIELD: chemistry.

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

FIELD: chemistry.

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

FIELD: chemistry.

SUBSTANCE: invention relates to a method of continuous catalytic production of methylmercaptan by reacting and hydrogen sulphide in gaseous phase at temperature ranging from 200 to 600°C and pressure ranging from 1.5 to 40 bars, involving a) distribution of the whole amount of catalyst on at least two separate zones, b) feeding a gaseous mixture containing methanol and hydrogen sulphide into the first zone, b) feeding methanol in liquid and/or gaseous state between the first, second and the next zones if they are present and c) separation of the formed methylmercaptan, wherein overall molar ratio of the used amount of hydrogen sulphide to methanol ranges from 1:1 to 10:1, and preferably from 1:1 to 5:1. Methymercaptan is an industrially important intermediate product, used in synthesis of methionine, as well as in production of dimethyl sufoxide and dimethyl sulfone.

EFFECT: production of methylmercaptan using a cost-effective method.

19 cl

FIELD: chemistry.

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

FIELD: chemistry.

SUBSTANCE: invention relates to a method for continuous production of methylmercaptan from hydrogen sulphide and methanol while directly obtaining hydrogen sulphide at the same time, for which the reaction mixture coming out of a hydrogen sulphide synthesis reactor under pressure is mixed with methanol and the obtained mixture is fed under pressure into a methylmercaptan synthesis reactor with creation of pressure difference between reactors used for both synthesis processes, under the effect of which the stream of the hydrogen sulphide and methanol mixture is forcibly moved towards the methylmercaptan synthesis reactor.

EFFECT: improved method for producing methylmercaptan which reduces power consumption and increases cost effectiveness of the process.

18 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention describes a method of producing alkylmercaptans via catalytic reaction between alkanols and hydrogen sulphide in gas phase on alkali metal tungstates, while carrying out said reaction in at least two successive reaction zones containing catalysts with different activity and selectivity.

EFFECT: improved method.

18 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: described is a method of producing acrolein by dehydrating glycerol in the presence of tungsten compound-containing solid-phase catalysts with Hammett acidity H0 less than +2, which contain palladium as a promoter.

EFFECT: high output and enabling catalyst regeneration without loss of properties thereof.

23 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of continuous obtaining methylmercaptane by interaction of initial mixture, which contains dialkyl sulphides and dialkyl polysulphides, with hydrogen sulphide. Process is carried out in presence of catalyst based on Al2O3, SiO2, TiO2, alumosilicates, zeolites, bentonites or alumina, containing, at least, 1 wt % of alkali metal oxide, or catalyst, consisting of said compounds, in reactor with, at least, two separate catalyst-containing zones or in several successively placed reactors, and prevailing part or entire amount of said dialkyl sulphides and/or dialkyl polysulphides together with, at least, part of entire amount of used hydrogen sulphide is supplied into first catalyst-containing zone of reactor, and the remaining amount of hydrogen sulphide and dialkyl sulphides and/or dialkyl polysulphides is dosed into space between catalyst-containing zones, and initial gas mixture can also contain dialkyl ethers, which react with hydrogen sulphide with formation of alkylmercaptanes.

EFFECT: novel method of obtaining alkylmercaptanes with high selectivity is elaborated.

13 cl, 3 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: catalyst preparation method includes an oxide inorganic carrier material and an oxide composition containing oxygen together with at least one alkali metal and tungsten. The method comprises the following stages: 1) providing at least one oxide inorganic material of a carrier in the form of particles of less than 1000 mcm in size, an oxide compound of tungsten. The tungsten oxide compound is selected from the group consisting of tungsten trioxide (WO3), tungstic acid (WO3⋅H2O), metatungstic acid, paratungstic acid, isopolytungstic acids, heteropolytungstic acids, ammonium salts thererof, hydrates thereof and mixtures thereof and at least one separate alkali metal compound. At least one mentioned alkali metal compound is a basic alkali metal compound, 2) mixing the carrier material with an oxide tungsten compound and at least one separate alkali metal compound to form the catalyst composition, and 3) forming the resulting catalyst composition. A catalyst for obtaining alkylmercaptans and a method for obtaining alkylmercaptans are also proposed.

EFFECT: invention allows to obtain a catalyst which exhibits improved activity and selectivity in the reaction of hydrogen sulphide with alkanols to produce alkylmercaptans.

18 cl, 23 dwg, 5 tbl, 18 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides catalyst for production of methyl ethyl ketone via oxidation of n-butenes by oxygen and/or oxygen-containing gas, which catalyst is composed of aqueous solution of molybdeno-vanado-phosphoric heteropolyacid or mixture of the latter with its salt and 5·10-4 to 1·10-2 M palladium stabilized by phthalocyanine ligand at palladium-to-phthalocyanine molar ratio 0.5-2. Mo-V-phosphoric heteropolyacid is depicted by formula H19P3Mo18V7O84. concentration of vanadium being 0.4 to 2.2 g-atom/L. Oxidation of n-butenes is carried out continuously in two steps at temperature 15 to 90оС. Catalyst is regenerated in contact with oxygen or oxygen-containing gas at 140-190оС and oxygen pressure 1-10 gauge atm.

EFFECT: enhanced process efficiency due to increased stability of catalyst components.

7 cl, 1 dwg, 6 tbl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: catalyst is prepared by impregnating alumina with cobalt chloride solution followed by drying and activation, the latter being effected by treating catalyst first with hydrogen sulfide/hydrogen mixture at 380-420оС and then with hydrogen at 200-260оС. Invention also provides catalyst for production methylmercaptan through hydrogenolysis of dimethyl sulfide containing 8.0-15.0% cobalt sulfide applied onto alumina treated by above-indicated method. Process is carried out at dimethyl sulfide supply velocity 13.4 to 128.7 mole/h per 1 g catalyst.

EFFECT: increased methylmercaptan production productivity.

3 cl, 1 tbl, 15 ex

FIELD: analytical methods in petroleum industry.

SUBSTANCE: invention relates to analytical checking of crude oil, petroleum derivatives, and gas condensate quality. 2 to 5g sample is thermostatically controlled at 50-70°C, while simultaneously hydrogen sulfide and light mercaptans are for 2-5 min displaced by inert gas or air into in series arranged absorption solutions, namely sodium carbonate solution for determining hydrogen sulfide and sodium hydroxide solution for determining light mercaptans. After complete withdrawal of hydrogen sulfide and light mercaptans, their quantitative content is determined by means of iodometric titration method.

EFFECT: extended range of analyzed products, increased determination accuracy, shortened analytical procedure, and enabled carrying out analyses not only in stationary laboratory without deviation from standardized procedures.

1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of continuous catalytic production of methylmercaptan by reacting and hydrogen sulphide in gaseous phase at temperature ranging from 200 to 600°C and pressure ranging from 1.5 to 40 bars, involving a) distribution of the whole amount of catalyst on at least two separate zones, b) feeding a gaseous mixture containing methanol and hydrogen sulphide into the first zone, b) feeding methanol in liquid and/or gaseous state between the first, second and the next zones if they are present and c) separation of the formed methylmercaptan, wherein overall molar ratio of the used amount of hydrogen sulphide to methanol ranges from 1:1 to 10:1, and preferably from 1:1 to 5:1. Methymercaptan is an industrially important intermediate product, used in synthesis of methionine, as well as in production of dimethyl sufoxide and dimethyl sulfone.

EFFECT: production of methylmercaptan using a cost-effective method.

19 cl

FIELD: chemistry.

SUBSTANCE: present invention relates to a continuous method of producing methylmercaptan which is a valuable organic synthesis intermediate product. The proposed method involves obtaining methylmercaptan through contact of a thoroughly mixed mixture of oxides of carbon, sulphur or hydrogen sulphide and hydrogen at high temperature and pressure in the presence of a moulded solid catalyst which contains K2MoO4 as an active component, an active promoter, where the active promoter is a mixture of oxides or a mixture of sulphides or a mixture of sulphides and oxides of metals selected from a group consisting of iron, cobalt, nickel, lanthanum, cerium and manganese and optionally a carrier.

EFFECT: preparation of a new catalyst for obtaining methylmercaptan and a method which uses this catalyst, which increases methylmercaptan output.

37 cl, 6 ex, 5 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of dimethylsulphide through conversion of dimethyldisulphide in the presence of a catalyst - aluminium oxide, at atmospheric pressure and temperature of 250-400°C with addition of methanol to the reaction mixture in amount of 0.17-0.82 g per 1 g of the initial dimethyldisulphide.

EFFECT: increased selectivity of formation of dimethylsulphide which is used as an odorant and starting material in synthesis of dimethylsulphoxide which is used as a medicinal agent, solvent and extraction agent.

3 cl, 1 tbl, 21 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for continuous production of methylmercaptan from hydrogen sulphide and methanol while directly obtaining hydrogen sulphide at the same time, for which the reaction mixture coming out of a hydrogen sulphide synthesis reactor under pressure is mixed with methanol and the obtained mixture is fed under pressure into a methylmercaptan synthesis reactor with creation of pressure difference between reactors used for both synthesis processes, under the effect of which the stream of the hydrogen sulphide and methanol mixture is forcibly moved towards the methylmercaptan synthesis reactor.

EFFECT: improved method for producing methylmercaptan which reduces power consumption and increases cost effectiveness of the process.

18 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst and to a method to produce methyl mercaptan in its presence. A catalyst is described on a carrier, which contains a) compound of molybdenum and potassium as active components, besides, molybdenum and potassium may represent components of a single compound; b) a promotor including TeO2, and c) oxide carrier. The method to produce methyl mercaptan is described in catalytic process by reaction of carbon oxides, for instance, CO, CO2, or their mixtures, sulfur and/or hydrogen sulfide, and hydrogen, in which the reaction takes place in presence of the above described catalyst.

EFFECT: increased activity of catalyst.

12 cl, 1 tbl, 1 dwg, 9 ex

FIELD: chemistry.

SUBSTANCE: invention describes a method of producing alkylmercaptans via catalytic reaction between alkanols and hydrogen sulphide in gas phase on alkali metal tungstates, while carrying out said reaction in at least two successive reaction zones containing catalysts with different activity and selectivity.

EFFECT: improved method.

18 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry. The method involves reaction of C60-fullerene with 1-[2-(methylsulphanyl)ethyl]diazoacetic ether in o-dichlorobenzene (o-DCB) in the presence of a three-component catalyst {Pd(acac)2:4PPh3:4Et3Al} at temperature 80°C for 0.2-1.0 hours. 1'-[2-(methylsulphanyl)-ethyl]-1'-ethylformylcyclopropa[2',3':1,9](C60-Ih)[5,6]fullerene (1) is obtained with output 31-55%.

EFFECT: obtaining functionally substituted fullerenes, which can be used as effective nanocomponent additives to industrial oil, as well as novel optoelectronic materials.

1 cl, 1 tbl, 1 ex

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