Catalysts containing halide-containing tungstates of alkali metals for synthesis of alkylmercaptans and preparation methods thereof

FIELD: chemistry.

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

 

The present invention relates to a catalyst which contains galogensoderjasimi wolframate alkali metals and which is used for the synthesis of allylmercaptan of alkanols and hydrogen sulfide, as well as to a method for preparing such a catalyst.

The term "alkali metal" refers associated alkali metals according to the Periodic system of elements, with wolframite can also contain two or more different corresponding alkali metals. The term "halide" refers to linked halogen-free Periodic system of elements, with the invention of wolframite alkali metals can also contain two or more different halides.

Under allylmercaptan means primarily mercaptan, which is an important industrial intermediate product that is used, for example, for the synthesis of methionine, as well as for the synthesis of dimethyl sulfoxide and dimethyl sulfone. The mercaptan currently mainly produced from methanol and hydrogen sulfide by conducting the reaction between the catalyst is aluminum oxide. The mercaptan is usually synthesized in the gas phase at a temperature in the range from 300 to 500°C. and at a pressure in the range from 1 to 25 bar.

During the synthesis of methylmercaptan the reaction mixture along with the resulting metalmark the tan contains unreacted educt and by-products, such as dimethyl sulphide and dimethyl ether, as well as inert in the reaction conditions, gases, such as methane, carbon monoxide, hydrogen and nitrogen. The resulting mercaptan is separated from this reaction mixture.

To ensure the economic efficiency of the production of methylmercaptan catalytic reaction of methanol with hydrogen sulfide should proceed with the highest output in order to maintain the cost of separation of the resulting mercaptan from the reaction mixture at the lowest possible level. Significant costs are associated primarily with high energy consumption for cooling of the reaction mixture required for condensation of the contained mercaptan.

To improve the activity and selectivity of the catalyst is aluminum oxide is usually mixed, using it as a carrier, with tungstate, potassium or cesium tungstate. While the tungstate is usually used in an amount up to 25 wt.% in terms of the total weight of the catalyst. To increase the activity and selectivity of the catalyst can also by increasing the molar ratio between hydrogen sulfide and methanol. Usually they are used in a molar ratio of from 1:1 to 10:1.

However, the high molar ratio between the reagents indicates the presence of hydrogen sulfide in the reaction is ionic mixture in a large excess and thereby connected with the necessity of constant returns in the production cycle of large volumes of gas. Therefore, to reduce the amount of necessary energy ratio between hydrogen sulfide and methanol should only be slightly different from 1:1.

In the patent US 2820062 method for obtaining organic thiols using catalysts based on activated alumina, mixed with potassium tungstate in an amount of from 1.5 to 15 wt.% in terms of the total mass of catalyst. This catalyst has a high activity and selectivity when the reaction temperature of 400°C and the molar ratio between the reactants is equal to 2:1. In the description to the specified patent discusses various possibilities for the introduction of potassium tungstate in the aluminum oxide. Thus, in particular, for this purpose can be used in methods of impregnation of alumina with potassium tungstate, methods of coprecipitation and simple mixing them. Actually the technology of preparation of the catalyst is not significant for the economic efficiency of the process of synthesis of methylmercaptan.

In EP 0832687 B1 describes the benefits associated with use as a promoter of tungstate cesium (Cs2WO4instead of tungstate, potassium (K2WO4). Thus, in particular, the use of caesium tungstate allows you to increase the activity of the catalyst while simultaneously achieving good selectivity.

Increase the concentration is tion of caesium tungstate to the values to about 40 wt.%, allows you to increase the selectivity of the catalyst upon receipt of the mercaptan to the values, reaching 92%, without too significant reduction in catalyst activity.

According to common opinion, the best selectivity have catalysts, in which the ratio between alkali metal and tungsten is 2:1 (A.V.Mashkina and others, React. Kinet. Catal. Lett., T.36, No. 1, 1988, cc.159-164).

The present invention was based on the task to provide the catalyst at low molar ratios between hydrogen sulfide and methanol would have higher activity and selectivity compared with the known catalysts, and thus would allow to increase the output of allylmercaptan and economic efficiency of their production process, and to suggest a method of preparing such a catalyst.

This problem is solved by using a catalyst which contains a catalytically active alkali metal tungstate containing primarily associated alkali metals and tungsten in a molar ratio between the alkali metals and tungsten less than 4:1, especially from 3:1 to 0.9:1, preferably from 2.4:1 to 1:1, particularly preferably from 2.2:1 to 1.2:1, and the halide(s), especially the halides and alkali metals in a molar ratio of from 0.01:1 to 3:1, preferably from 0.01:1 to 1:1, the OS is especially preferably from 0.1:1 to 1:1.

Proposed in the invention the catalytically active galogensoderjasimi compound has the following General formula

,

in which

A denotes at least one alkaline metal, first of all

selected from the group comprising Na, K, Cs and Rb;

X denotes at least one halide selected from the group comprising F, Cl, Br and I;

x denotes a number in the range from 0.9 to less than 4, especially from 1, 2 to 3;

y has a value that depends on the structure of tungstate and content

alkali metal with a 6-valence tungsten

z denotes a number in the range from 0.01 to less than 12, especially in the range from 0.9 to 4.

The value of the index z is a measure of the content of halogen in the tungstate, with whom he should not be bound chemically.

Halide component in the compound of formula I consists of or contains primarily chloride in cases where the composition of the tungstate comprises at least two different corresponding alkali metal and/or at least one halide selected from the group comprising F, Br and I.

Chloride should preferably be present as the sole halide in those cases, when the molar ratio of Na or K and W in the catalyst is from over 0.9 to 1.9.

Melodramaticheskiy component catalic the Cesky active compounds can consist of one or more elements of the group of alkali metals. Likewise linked halide component of the catalyst may also comprise one or more different halides.

Content galogensoderjasimi of alkali metal tungstate in the proposed invention the catalyst, when it is presented in the form of deposited catalyst is from 8 to 50 wt.%, first of all, from 15 to 40 wt.%, preferably from 20 to 36 wt.%. The catalyst in the form of "core-shell" given amounts relate to its shell.

For the preparation of the catalyst galogensoderjasimi oxide compounds of alkali(s) metal(s) and tungsten can be directly impregnated molded carrier (with the receipt of the deposited catalyst).

For the preparation of catalysts in the form of extrudates or extruded products (tablets) proposed in the invention of the oxide composition impregnated or mixed powder carrier, after which the intermediate product is subjected to molding (obtaining a solid catalyst). The preparation of the catalyst in the form of "core-shell" catalytically active composition is impregnated with a powdered carrier and then the obtained mixture is applied in the form of a shell on the core carrier, preferably of inert material.

The ratio between the halide(s) and Molochny the(s) metal(s) should preferably lie in the range from 0.1:1 to 1:1. In accordance with this proposed invention wolframate used in the synthesis of allylmercaptan obtained by the interaction of alkanols with hydrogen sulfide, in contrast to the known from the prior art impregnated with cesium tungstate (Cs2WO4or tungstate, potassium (K2WO4) catalysts include halides in the appropriate quantity.

In the claimed invention, it was found that the presence of halides in the tungstate primarily on preferably used as a carrier of aluminum oxide allows comparison with the applied according to the prior art, is not solely containing the halide of the alkali metal tungstate to give a catalyst of higher activity with high selectivity. In addition, the addition of halides to the alkali metal tungstate unexpectedly allows to achieve extremely high selectivity of the catalyst at a particularly high degree of conversion of the alcohol. According to the invention with a very high content in the catalyst promoter can achieve an exceptionally high degree of transformation of the original substance without known from the prior art for not containing halide catalysts reduce the selectivity of the catalyst. In addition, when the invention it was found that by varying soothes the tion between alkaline(s) metal(s), tungsten and halogen(s), and the choice of alkali metals and halides can be targeted to regulate the activity and selectivity of the catalyst. The ability to use mixtures of different compounds of alkali metals or Halogens allows, in addition, at least partially replace the relatively expensive materials, such as compounds of cesium, rubidium, bromine or iodine, at a cheaper substances, such as compounds of potassium or sodium, or chloride without compromising the activity or selectivity of the catalyst.

Proposed in the invention, the catalyst preferably used in the form of deposited catalyst, the surface of the carrier which is impregnated with a catalytically active substance, or as a catalyst in the form of "core-shell", in which the core, preferably of inert material is enclosed in a shell of a mixture of catalytically active substances and substance carrier. In addition, you can also use proposed in the invention catalyst in the form of extrudates or extruded products, before forming which the catalytically active substance is mixed with a powder substance carrier, respectively impregnate his catalytically active substance. As substances vehicles for such catalysts use zvezdnye oxide inorganic compounds, such as SiO2, Tio2, ZrO2and preferably so-called activated alumina. The latter has a large specific surface area in the range of from about 10 to 400 m2/g and consists mainly of oxides of the transition series of crystallographic phases of aluminum oxide (see, for example, Ullmann's Enzyclopedia of Industrial Chemistry, 1985, .Al, cc. 561-562). Such oxides of transition modifications include γ-, δ-, η-, κ-, x - and θ-alumina. All these crystallographic phase of aluminum oxide by heating to temperatures above 1100°C become thermally stable α-alumina. Designed for use as a catalyst carrier activated alumina are now widely available on the market in the form of a commercially available product of various varieties and forms. For the preparation of supported catalysts are most suitable granular or extruded molded product carrier of aluminum oxide with a diameter of grains from 1 to 5 mm, a specific surface area of from 180 to 400 m2/g, a total pore volume from 0.3 to 1.2 ml/g and a bulk density of 300 to 900 g/l To prepare proposed in the invention catalyst, it is preferable to use aluminum oxide with a specific surface area of more than 200 m2/g, because with increasing specific surface area of the aluminum oxide is I am somewhat increases the catalytic activity of the finished catalyst. Such material is preferably used in powder form for the preparation of catalysts with the structure of "core-shell", catalysts in the form of extrudates or catalysts in the form of extruded products (preformed catalysts).

According to the invention the substance carrier is usually not subjected to pre-treatment halogenation acid.

Aqueous impregnating solution for the application of the promoter can be prepared in a simple way from water-soluble compounds of alkali metals, compounds of tungsten and compounds of halogen, primarily of tungsten acid (H2WO4), hydroxides of alkali metals, halides of alkali metals and in some cases ammonium halides or halogenation acid. For this purpose, for example, tungstic acid are suspended in water and dissolved by adding a base and heating. Required(e) halide(s) of the alkaline(-s) metal(s) or ammonium halides, and optionally the corresponding hydroxides and/or, for example, halogenation acid with the desired halide also dissolved in water and the resulting solution was combined with a solution of tungstic acid (obtaining a solution of the promoter) in such proportions that the ratio between wolframate alkali metals contained in them halide is mi in the final composition corresponded to the desired one. Along with halides of alkali metals likewise preferably also the use of salts of alkali metals, anions (salts) can no residue removed by calcination and as an example which can be called nitrates, formate, oxalates, acetates or carbonates. For stabilization of the solution of the promoter with a pH in the range from 8 to 14 suitable inorganic and organic bases. It is preferable to use those foundations, which can no residue removed by a final calcination obtained after impregnation of the catalyst. For your preferred reason of this kind include ammonium hydroxide, and organic bases, especially amines.

This approach is usually possible to neutralize at least about 75%, or even almost all 100% of the acidic groups present on the surface of the substances of media such as Al2O3.

The molar ratio between the compounds of alkali metals and halides in the preparation of an aqueous impregnating solution is chosen so that the molar ratio between the halides and alkali metals in the new proposed invention wolframate was from 0.01:1 to 3:1. This requirement results in the application proposed in the invention catalysts for significant than the s with known does not contain halides as catalysts for increasing yield, especially at low ratios between hydrogen sulfide and methanol in the reaction gas.

For your preferred wolframates include wolframite cesium, potassium and rubidium, primarily wolframate cesium, and to the preferred halides include fluoride, bromide and chloride primarily fluoride and bromide.

Wolframate with different cations of alkali metals or with different content of different halides preferably should contain cations of two different alkali metal and at least one halide in the ratio between alkaline(s) metal(s) and halogen in the range from 0.01:1.0 to 3.0:1.0, with the molar quantity of alkali metals, respectively, may present several different halides are calculated in the form of their respective total amounts. The relative content of cheaper alkali metal or halide increase and decrease of the relative content is relatively more expensive alkali metal or halide to a level which is still no evidence of any deterioration in activity or selectivity of the catalyst.

When using combinations of alkali metals preferred wolframate in which cesium or rubidium component is replaced in p is imushestvenno proportion of potassium or sodium cations.

To preferred catalysts include the following combinations corresponding alkali metals, including and other than 1:1 ratio between them:

a) potassium and cesium,

b) sodium and cesium,

C) rubidium and cesium,

d) sodium and potassium,

d) rubidium and potassium.

For applying the solution of the promoter on the carrier you can use different methods of impregnation, as an example, which can be called impregnation by immersion, impregnation, spraying, vacuum impregnation and impregnation with filling of pore volume, which can also be repeated several times. When the impregnated molded carrier selected method of impregnation should provide the possibility of saturation of the molded product carrier promoter to the desired degree with high uniformity of its distribution throughout the cross section of each of the molded products of the media.

The solution of the promoter is preferably applied to a molded product carrier by impregnation by spraying or vacuum impregnation in one or two stages. Impregnation by spraying an aqueous impregnating solution spray (sprayed) on the molded product carriers. During vacuum impregnation in the completed molded products native capacity first vacuum pump creates a vacuum. Then after opening the shut-off valves for connecting the Lange, intended for submission to the capacity of the aqueous impregnating solution, it is absorbed into the container until then, until you cover the entire inside of the bulk layer molded carriers. Upon completion of the impregnation, lasting from 0.2 to 2 hours, not absorbed by the material of the molded carrier solution is lowered or drained from the container.

The initial gradient of the concentration of promoter in cross-section molded carrier can be almost completely levelled by pre-drying at room temperature for 1-10 hours in This way can improve the uniformity of the promoter in cross-section it has impregnated catalyst particles. Pre-cooked in this way the catalyst is then to remove the residual moisture is dried at a temperature in the range from 100 to 200°C., preferably from 100 to 140°C. for 1-10 hours After that, the catalyst was calcined for 1-20 hours, preferably 1-5 hours at a temperature in the range from 300 to 600°C., preferably from 420 to 480°C. by annealing the promoter is fixed on the aluminum oxide, and is contained in the impregnating solution, the base is decomposed and removed. In the process of pre-drying, drying and calcination through the granular layer of the molded carrier pre-prepared catalyst is battelino you can skip the gas stream, what contributes to the removal of the catalyst residual moisture and gaseous decomposition products of the grounds.

The impregnated molded carrier can also be carried out in several stages, primarily in two stages. In this case, in one of the preferred options in the first stage impregnation using an impregnating solution containing compounds of the alkaline(-s) metal(s) and tungsten in amounts of one to two thirds of their total intended for impregnation amount. If sequential, but at least the two-stage impregnation molded carrier prior to the first stage catalyst in some cases, the annealing is not exposed. Otherwise, the second stage performs the same sequence of impregnation molded carrier, drying and calcination as in their one-step impregnation.

Such multi-stage impregnation process, it is advisable to use primarily in the case when it is necessary to provide a high concentration of promoter in the catalyst and/or when the limited solubility of the mixture components of the promoter fails to achieve the required content in the catalyst for one-stage impregnation.

In addition to moulded products-carriers, respectively, the substance is a carrier, it is possible to process them, accordingly, the impregnation stage (stage a) stated in article 22 of the claims method, repeatedly spraying the treatment solution and after each stage of spraying the treatment solution on the molded product carriers, respectively, substance-carrier partially removed from them, from him, before carrying out stage b) residual moisture at temperatures up to 120°C.

The preparation of the catalyst in the form of "core-shell" applied as shell powder before or after its application to the core subjected to calcination. The catalyst of this type can be prepared, for example in accordance with EP-B-0068193. In the preparation of catalysts in the form of extrudates or pressed powder products can also be subjected to annealing before and/or after its formation.

Examples

Example 1 (comparative)

150 g of aluminium oxide (product Spheralite 501 (A) was impregnated to 21.0 wt.% tungstate cesium (Cs2,0WO4by vacuum impregnation. The impregnation was carried out, in particular, as follows.

To prepare an impregnating solution of 55.7 g of tungstic acid suspended in 44,5 g of water and dissolved by adding byr111.4 g of 25%ammonia solution and heated to 50°C. In 37,3 g of water was dissolved 74,6 g Cs(OH)•H2O and the resulting solution was mixed with the first solution with a solution of tungstic acid). Then the resulting solution was stirred in a closed beaker within 48 hours After that, the volume of solution by adding 25 g of water was brought to 234 ml

In a glass vessel, vakuumirovaniya to a residual pressure of 150 mbar, put the aluminum oxide. After this was opened by the corresponding valve in the feed line impregnating solution, which is absorbed in vakuumirovaniya glass vessel to fully cover them all bulk layer in a glass vessel with a moulded products. After a 15 minute exposure and fill the glass vessel air is not absorbed by the aluminum oxide impregnation solution was poured back into the chemical glass. The amount of absorbed aluminum oxide impregnation solution was with 79 ml

Next, the granules were dried for 1 h at room temperature in a stream of air, and then to remove the residual moisture was dried for 3 h at 120°C. thereafter, the granules were progulivali for 3 h at 455°C.

Example 2 (comparative)

In this example, repeating the procedure described in comparative example 1, but in contrast, the alumina was impregnated to 26.3 wt.% of caesium tungstate

(Cs2,0WO4).

Example 3 (comparative)

In this example, repeating the procedure described in comparative example 1, but in contrast, the alumina was impregnated at 19.6 wt.% wills is ramata potassium

(K2,0WO4) using CON instead of Cs(OH)•H2O.

Example 4

150 g of aluminium oxide (product Spheralite 501 (A) impregnated 22.3 wt.% fluoride containing cesium tungstate by vacuum impregnation. The impregnation was carried out, in particular, as follows.

To prepare an impregnating solution of 56.8 g of tungstic acid suspended 45.4 g of water and dissolved by adding 113,6 g of 25%ammonia solution and heated to 50°C. In 40.0 g of water was dissolved 68,8 g CsF and the resulting solution was mixed with the first solution (solution of tungstic acid). Then the resulting solution was stirred in a closed beaker for 4 hours After that, the volume of solution added to it 24,9 g of water was brought to 234 ml

In a glass vessel, vakuumirovaniya to a residual pressure of 150 mbar, put the aluminum oxide. After this was opened by the corresponding valve in the feed line impregnating solution, which is absorbed in vakuumirovaniya glass vessel to fully cover them all bulk layer in a glass vessel with a moulded products. After a 15 minute exposure and fill the glass vessel air is not absorbed by the aluminum oxide impregnation solution was poured back into the chemical glass. The amount of absorbed aluminum oxide impregnation solution was in 73 ml.

Next, the granulate was dried in a t is the significance of 1 h at room temperature in a stream of air, and then to remove the residual moisture was dried for 3 h at 120°C. thereafter, the granules were progulivali for 3 h at 455°C.

Example 5

150 g of aluminium oxide (product Spheralite 501 (A) was soaked in total of 23.9 wt.% chloride-containing cesium tungstate by vacuum impregnation. The impregnation was carried out, in particular, as follows.

To prepare an impregnating solution of 57.8 g of tungstic acid suspended in 46.2 g of water and dissolved by adding 115,6 g of 25%ammonia solution and heated to 50°C. and 30.0 g of water was dissolved and 77.6 g of CsCl and the resulting solution was mixed with the first solution (solution of tungstic acid). Then the resulting solution was stirred in a closed beaker for 22 hours After that, the volume of solution by the addition thereto of 23.2 g of water was brought to 234 ml

In a glass vessel, vakuumirovaniya to a residual pressure of 150 mbar, put the aluminum oxide. After this was opened by the corresponding valve in the feed line impregnating solution, which is absorbed in vakuumirovaniya glass vessel to fully cover them all bulk layer in a glass vessel with a moulded products. After a 15 minute exposure and fill the glass vessel air is not absorbed by the aluminum oxide impregnation solution was poured back into the chemical glass. The amount absorbed in the oxide and uminia impregnating solution was 74 ml

Next, the granules were dried for 1 h at room temperature and then for 3 h at 120°C, after which he progulivali for 3 h at 455°C.

Example 6

150 g of aluminium oxide (product Spheralite 501 (A) was soaked in total of 18.5 wt.% broadstraik of caesium tungstate by two-stage vacuum impregnation. The impregnation was carried out, in particular, as follows.

To prepare an impregnating solution of 58.5 g of tungstic acid suspended in of 46.8 g of water and dissolved by adding 116,9 g of 25%ammonia solution and heated to 50°C. and 30.0 g of water was dissolved 15.6 g CsBr and 50.4 g of Cs(OH)•H2O and the resulting solution was mixed with the first solution (solution of tungstic acid). Then the resulting solution was stirred in a closed beaker within 21 hours After that, the volume of solution by the addition thereto of 17.2 g of water was brought to 234 ml

In a glass vessel, vakuumirovaniya to a residual pressure of 150 mbar, put the aluminum oxide. After this was opened by the corresponding valve in the feed line impregnating solution, which is absorbed in vakuumirovaniya glass vessel to fully cover them all bulk layer in a glass vessel with a moulded products. After a 15 minute exposure and fill the glass vessel air is not absorbed by the aluminum oxide impregnation solution was poured back in hee is practical glass. The amount of absorbed aluminum oxide impregnation solution was 81 ml

Next, the granules were dried for 1 h at room temperature and then for 3 h at 120°C, after which he progulivali for 3 h at 455°C.

Example 7

150 g of aluminium oxide (product Spheralite 501 (A) was soaked in total of 29.6 wt.% modestiae of caesium tungstate by vacuum impregnation. The impregnation was carried out, in particular, as follows.

To prepare an impregnating solution 64,1 g tungstic acid suspended in a 51.3 g of water and dissolved by adding 128,2 g of 25%ammonia solution and heated to 50°C. and 30.0 g of water was dissolved 132,7 g CsI and the resulting solution was mixed with the first solution (solution of tungstic acid). Then the resulting solution was stirred in a closed beaker for 6 hours After that, the volume of solution by adding 6 g of water was brought to 234 ml

In a glass vessel, vakuumirovaniya to a residual pressure of 150 mbar, put the aluminum oxide. After this was opened by the corresponding valve in the feed line impregnating solution, which is absorbed in vakuumirovaniya glass vessel to fully cover them all bulk layer in a glass vessel with a moulded products. After a 15 minute exposure and fill the glass vessel air is not absorbed by the oxide of aluminum is I impregnating solution was poured back into the chemical glass. The amount of absorbed aluminum oxide impregnation solution was 80 ml.

Next, the granules were dried for 1 h at room temperature and then for 3 h at 120°C, after which he progulivali for 3 h at 455°C.

Example 8

95 g of aluminum oxide (product Spheralite 501 (A) was soaked in total, 23.5 wt.% fluoride and broadstraik of caesium tungstate by vacuum impregnation. The impregnation was carried out, in particular, as follows.

For preparation of the impregnating solution to 36.8 g of tungstic acid suspended in 35.0 g of water and dissolved by adding 73,6 g of 25%ammonia solution and heated to 50°C. and 30.0 g of water was dissolved 22,3 g CsF and 31.2 g of CsBr and the resulting solution was mixed with the first solution (solution of tungstic acid). Then the resulting solution was stirred in a closed beaker for 22 hours then the volume of the solution by adding thereto 1 g of water brought up to 234 ml

In a glass vessel, vakuumirovaniya to a residual pressure of 150 mbar, put the aluminum oxide. After this was opened by the corresponding valve in the feed line impregnating solution, which is absorbed in vakuumirovaniya glass vessel to fully cover them all bulk layer in a glass vessel with a moulded products. After a 15 minute exposure and fill the glass vessel air not pitann the second aluminum oxide impregnation solution was poured back into the chemical glass. The amount of absorbed aluminum oxide impregnation solution was thus 44 ml.

Next, the granules were dried for 1 h at room temperature and then for 3 h at 120°C, after which he progulivali for 3 h at 455°C.

Example 9 (example application)

Obtained in the above examples, the catalysts were investigated on their performance in the synthesis of mercaptan from hydrogen sulfide and methanol.

The synthesis in each case carried out in a tube of stainless steel inner diameter of 18 mm and a length of 500 mm, a Bulk layer of each of the catalysts with the volume of 76 ml were fixed with both ends of the reaction tubes Packed layers of glass balls, which are used as inert filler. The reaction tube was heated to the reaction temperature of approximately 320°C., passed through a double jacket thermal oil heat transfer medium.

The experiments were conducted under the following conditions:

hourly average gas flow rate:1300 h-1(under normal conditions)
average hourly feed rate of the liquid:0,84 h-1(in terms of liquid Meon)
the reaction temperature:320°C
the mass ratio of H2S/MeOH:1,9
pressure:9 bar

The reaction mixture containing the reaction products: methyl mercaptan, dimethyl sulphide and dimethyl ether and unreacted educt methanol and hydrogen sulfide was analyzed by gas chromatography directly during the reaction.

Adding to the catalyst halides observed a significant increase in the activity of the catalyst while increasing its selectivity. In contrast to the known from the prior art catalysts, the selectivity of which is reduced, in particular, at high degrees of chemical conversion, selectivity proposed in the invention catalysts by adding to them halides still remains high even at high degrees of chemical transformations. Due to this increase in the output of methylmercaptan in comparison with the prior art reaches 15%. The selectivity of the catalyst can be increased to values of about 96.6 percent by regulating relations in it between the alkali metal, tungsten and halogen. When the industrial synthesis of methylmercaptan such improved properties of the catalyst also provides significant cost savings, zatragivaemyh separating the reaction product from unreacted methanol and by-products.

In addition, the results obtained using the proposed in the invention catalysts of the above examples suggest the possibility of at least partial replacement of the halides of one another that can specifically regulate the activity and selectivity of the catalyst or to reduce the cost of raw materials used to prepare the catalysts.

Table 1:
The results of experiments
CatalystMol. the ratio of alkali metal/WHalogenMol. the ratio of halogen/alkaline metalThe content of the promoter [wt.%]The degree of conversion of methanol [%]Selectivity [%]Output [%]
SP12:1-021,082,493,376,9
SP2:1- 026,379,594,7to 75.2
SP32:1-019,676,0for 95.272,4
Ave. 42:1F1:122,375,496,672,8
Ave. 52:1C11:123,995,093,789,0
Ave. 6of 1.6:1VG0,2:118,592,494,5of 87.3
Ave. 72:1I1:129,688,995,5 84,9
Ave. 82:1F, VG1:123,591,496,688,3
Notes:
SP denotes "comparative example".

1. A catalyst containing an alkali metal tungstate containing at least one halide, and alkali-metal component selected from the group including Cs, Rb, or under the alkali-metal component refers to the combination of two related alkali metals, including and other than 1:1 ratio between them, selected from the group including
a) potassium and cesium,
b) sodium and cesium,
C) rubidium and cesium.

2. The catalyst according to claim 1, wherein the tungstate contains two corresponding alkali metal and at least one halide selected from the group comprising F, Cl, Br and I.

3. The catalyst according to claim 1, wherein the tungstate contains one halide selected from the group comprising F, Br and I.

4. The catalyst according to claim 1, wherein the tungstate contains two halide selected from the group comprising F, Cl, Br and I.

5. The catalyst according to one of claims 1 to 4, in which the tungstate contains at least one associated method, is Nochnoi metal, tungsten and at least one halide in a molar ratio between all of the alkali metals and tungsten from 0.9 to less than 4:1 and the molar ratio between all halides and all alkaline metals from 0.01 to 3:1.

6. The catalyst according to claim 5, in which the tungstate contains at least one halide selected from the group comprising F, Cl, Br and I.

7. The catalyst according to claim 6, characterized in that the molar ratio of alkali(s) metal(s) and tungsten in galogensoderjasimi the alkali metal tungstate is from 2.2:1 to 0.9:1 and the molar ratio of halide(s) and alkaline(s) metal(s) is from 1:1 to 0.01:1.

8. The catalyst according to one of claims 1 to 4, containing the substance carrier and galogensoderjasimi tungstate.

9. The catalyst according to claim 5, containing the substance carrier and galogensoderjasimi tungstate.

10. The catalyst according to claim 8, characterized by the presence of a substance in a carrier that does not contain halogenation acid.

11. The catalyst according to claim 8, representing a catalyst in the form of "core-shell", in which his heart as substance carrier is enclosed in a shell of galogensoderjasimi of alkali metal tungstate or impregnated this galogensoderjasimi the alkali metal tungstate substance carrier.

12. The catalyst according to claim 8, predstavlyayushie is a solid catalyst, in which substance-impregnated carrier galogensoderjasimi the alkali metal tungstate.

13. The catalyst according to claim 10, comprising a molded substance carrier, the surface of which is impregnated with a catalytically active oxide composition of the alkali metal tungstate and halides in a molar ratio between the alkali(s) metal(s) and tungsten from 0.9 to less than 4:1 and the molar ratio of halide(s) and alkaline(s) metal(s) from 0.01 to 3:1.

14. The catalyst according to one of claims 1 to 4, characterized in that the tungstate corresponds to the following General formula (I):

where And denotes at least one alkaline metal,
X represents at least one halogen,
x denotes a number from 0.9 to less than 4,
y denotes an oxygen content in the oxide and
z represents a number from 0.01 to less than 12.

15. The catalyst PP and 13, characterized in that it contains galogensoderjasimi the alkali metal tungstate in an amount of from 8 to 50 wt.%, preferably from 20 to 36 wt.%.

16. The catalyst according to one of PP-13, characterized in that the medium or substance carrier is an inorganic oxide compound.

17. The catalyst according to item 16, characterized in that the medium or substance carrier is an oxide of aluminum (Al2O3).

18. The catalyst according to claim 7, characterized in that the substance is a carrier has a specific surface area (determined by BET method) of from 180 to 400 m2/g and total pore volume from 0.3 to 1.2 ml/year

19. The catalyst according to one of claims 1 to 4, characterized in that the halide is selected from the group comprising F, Cl, Br and I.

20. The catalyst according to one of claims 1 to 4, characterized in that under the halides refers to at least two halide selected from the group comprising fluoride, chloride, bromide and iodide.

21. The way of cooking containing the alkali metal tungstate deposited catalyst, namely, that a) the holders or substance carrier is impregnated with an aqueous solution containing soluble compounds of alkali-metal component selected from the group including Cs, Rb, or alkali-metal component, which implies the combination of two related alkali metals, including and other than 1:1 ratio between them, selected from the group including
a) potassium and cesium,
b) sodium and cesium,
C) rubidium and cesium,
compounds of tungsten halide compounds in the required molar ratio between the alkali-metal component, the halide(s) and tungsten
b) the obtained impregnated molded carriers or obtained impregnated with highly dispersed substance-carrier (pre-cooked ka is alistar) is subjected to preliminary drying at room temperature,
C) if necessary, subjected to drying at a temperature of from 100 to 200°C to remove residual moisture,
g) is subjected to final annealing for 2-10 hours at a temperature of from 300 to 600°C and
d) get deposited catalyst or impregnated with highly dispersed substance-media content promoter of the total composition of AxWOycontent Xzwhere A, X, x, y and z have the above meanings, in the amount of from 8 to 50 wt.%, preferably from 20 to 36 wt.%, then
e) impregnated with highly dispersed substance-carrier suspended adding known auxiliary substances and applied to the core carrier of inert material or ekstragiruyut and pressed.

22. The method according to item 21, wherein the pH of the impregnating solution exceeds 7.

23. The method according to item 21, characterized in that at least once, repeat the execution of stages a)to C) and, if necessary, stage d).

24. The method according to item 21, wherein when multiple impregnation originally used impregnating solution contains from one to two thirds of the total anticipated number of compounds of alkali metals and compounds of tungsten.

25. The method according to item 23, wherein the media or substance-media repeatedly sprayed impregnating solution and after each stage spray propisochlor the solution to the media or the substance is a carrier of them, respectively from him before carrying out stage b) partially remove residual moisture at temperatures up to 120°C.

26. The method according to item 23, wherein the catalyst after the application of the impregnated substance-carrier on the core and after extrusion or pressing is subjected to heat treatment.

27. The method of producing allylmercaptan interaction alkanols with hydrogen sulfide in the presence of a catalyst according to one of claims 1 to 20.

28. The method according to item 27, which receive the mercaptan by the interaction of methanol with hydrogen sulfide.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis if 3-(methylthio)propanal and 2-hydroxy-4-(methylthio)butane nitrile through a catalytic reaction for respectively bonding methylmercaptan to acrolein and hydrocyanic acid to 3-(methylthio)propanal. In the said methods, the catalyst is heterogeneous, does not dissolve in the reaction medium and has formula (I) in which R1 and R2 represent hydrogen, alkyl with chain length from C1 to C12, and R1 can assume values different from R2, x is a number ranging from 0 to 6 and A represents a synthetic resin.

EFFECT: reduced material and technical expenses on production.

29 cl, 2 dwg, 2 ex

FIELD: isomerization and disproportionation catalysts.

SUBSTANCE: invention relates to crystalline α-chromium oxide, chromium-containing catalytic compositions, method for preparation thereof, and to a process of fluorine distribution in hydrocarbon and/or halogenated hydrocarbon in presence of indicated catalytic compositions. In claimed α-chromium oxide, about 0.05 to about 2 atomic % chromium in the lattice of α-chromium oxide is substituted by nickel atoms and, optionally, further chromium atoms in the lattice are substituted by trivalent cobalt atoms, the total amount of nickel and trivalent cobalt atoms in the α-chromium oxide lattice not exceeding 6 atomic %. Claimed α-chromium oxide is prepared via coprecipitation of solid substance by introducing ammonium hydroxide, this method being supplemented by introducing an excess of ammonium nitrate into precipitated mixture before dehydration step and calcination step at 375 to 1000°C in presence of oxygen. Chromium-containing catalytic compositions containing crystalline nickel-substituted α-chromium oxide as chromium-containing component optionally treated with fluorination agent are also claimed. Composition preparation procedure comprises: (a) coprecipitation of solid substance by introducing ammonium hydroxide into aqueous solution of soluble bivalent nickel salt, soluble trivalent chromium salt, and optionally soluble bi- or trivalent cobalt salt, wherein solution contains at least three moles nitrate per mole chromium and has concentration of nickel from about 0.05 to about 2 mol % based on total content of nickel, chromium, and cobalt (if present) in solution and total concentration of nickel and cobalt (if present) not higher than 6 mol % on the same basis; (b) collecting coprecipitated solid substance obtained in step (a); (c) drying collected solid substance; and (d) calcination of dried solid substance at 375 to 1000°C in presence of oxygen.

EFFECT: increased activity of catalytic composition in above-indicated processes.

15 cl, 8 dwg, 13 ex

FIELD: isomerization and disproportionation catalysts.

SUBSTANCE: invention relates to crystalline α-chromium oxide, chromium-containing catalytic compositions, methods for preparation thereof, and to a process of fluorine distribution in hydrocarbon and/or halogenated hydrocarbon in presence of indicated catalytic compositions. Claimed crystalline α-chromium oxide, wherein about 0.05 to about 6 atomic % chromium in the lattice of α-chromium oxide is substituted by trivalent cobalt (Co+3) atoms is via coprecipitation of solid substance by introducing ammonium hydroxide, this method being supplemented by introducing an excess of ammonium nitrate into precipitated mixture before dehydration step and calcination step at 375 to 1000°C in presence of oxygen. Chromium-containing catalytic compositions containing crystalline cobalt-substituted α-chromium oxide as chromium-containing component optionally treated with fluorination agent are also claimed. Composition preparation procedure comprises: (a) coprecipitation of solid substance by introducing ammonium hydroxide into aqueous solution of soluble cobalt salt and soluble trivalent chromium salt, wherein solution contains at least three moles nitrate per mole chromium and has concentration of cobalt from about 0.05 to about 6 mol % based on total content of cobalt and chromium in solution, followed by introducing into solution at least three moles ammonium per mole chromium; (b) collecting coprecipitated solid substance obtained in step (a); (c) drying collected solid substance; and (d) calcination of dried solid substance at 375 to 1000°C in presence of oxygen.

EFFECT: increased activity of catalytic composition in above-indicated processes.

15 cl, 8 dwg, 13 ex

The invention relates to catalytic chemistry, in particular to methods for khrommagnievogo catalyst gas-phase fluorination of kalogeropoulou, including for the synthesis of halocarbons

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 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: 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

FIELD: chemistry.

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

FIELD: chemistry.

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

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

The invention relates to a method of continuous hydration of ethylene, propylene or mixtures thereof with water in the vapor phase to the corresponding alcohols in the presence of salts heteroalicyclic as a catalyst at a molar ratio of water to olefin passing through the reactor, in the range of 0.1 to 3.0, an average hourly rate of gas supply water/olefin through the catalytic system 0,010 - 0.25 g/min/cm3concentrations of heteroalicyclic 5 to 60 wt.% from the total mass of the catalytic system, at a temperature of 150 - 350oC and a pressure ranging from 1000 to 25000 kPa

The invention relates to a catalyst used for the synthesis of mercaptan from methanol and hydrogen sulfide, as well as to a method for producing this catalyst

The invention relates to a catalyst for the synthesis of methylmercaptan and method thereof

FIELD: chemistry.

SUBSTANCE: invention relates to production of C3-C5 hydrocarbons through dehydrogenation of corresponding paraffin hydrocarbons n reactors with a fluid bed of micro-spherical chromia-alumina catalyst. Method is described for dehydrogenating C3-C5 paraffin hydrocarbons in fluid catalyst bed, containing oxides of chrome, potassium and a promoter, deposited on an alumina support which contains boehmite and up to 10 wt % hydrargillite, which is an aggregate in form of regular, including mimetic, and irregular double aggregates, consisting of hexagonal scaly crystals with size greater than 20 mcm.

EFFECT: increased efficiency of the process of dehydrogenating C3-C5 paraffin hydrocarbons, increased output of C3-C5 olefin hydrocarbons, reduced abrasive action on elements of a two-reactor installation for dehydrogenation when using chromia-alumina catalyst in a fluid bed.

5 cl, 2 tbl, 11 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: method of producing chlorine involves oxidation of hydrogen chloride at 270 to 370°C with molecular oxygen in the presence of a vanadium anhydride based catalyst. Components of the catalyst are lithium and potassium chlorides with the following ratio in wt % of the total mass of catalyst: KCl - 4 to 52, LiCl to 3-43, V2O5 - 15 to 85.

EFFECT: increased rate of oxidation of hydrogen chloride and reduced operating temperature.

9 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to the method of catalyst for phthalic anhydride production improvement or optimisation by the way of ortho-xilene and/or naphthalene vapour-phase oxidation. The said method includes the following stages: a) preparation of the initial catalyst containing at least the first layer positioned from the gas input side and the second layer positioned near the gas output with catalyst layers preferentially having the corresponding active mass containing the titanium oxide TiO2; b) partial change of the first layer for the catalyst prelayer having enhanced activity in order to obtain the improved catalyst. The improved catalyst obtained thereby, method for phthalic anhydride production and its application for phthalic anhydride production by the way of ortho-xilene and/or naphthalene vapour-phase oxidation are described also.

EFFECT: increase of the catalyst life cycle at constant or even increased product yield.

30 cl, 1 tbl, 1 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: group of inventions refers to supports (alumina support), to methods for making supports of catalysts activated in aerated layer and chrome-alumina catalyst for dehydrogenation of C3-C5 paraffin hydrocarbons to related olefines being monomers used for manufacturing of chemical rubbers, polymers, blending fuels. There is disclosed alumina support of boehmite morphology, specific surface 80 to 250 m2/g, pore size at least 0.2 cm3/g, microcrystallite size by coherent scattering region 500 to 3000 A. It contains interlayer water in amount corresponding to mole ratio aluminium oxide to water 0.8 to 1.2. There is described method for making support by high-temperature processing of hydrargillite in inert gas and/or ammonia, and/or carbon oxide medium at temperature 100 to 300°C and pressure 0.1 to 150 kgs/cm2 and following drying. Besides, there is disclosed method for making dehydrogenation catalyst of C3-C5 paraffin hydrocarbons by impregnation of support produced as described above with precursor solutions of chrome oxide, potassium oxide and activating agent representing, at least, one oxide chosen from the group: copper oxide, zinc oxide, manganous oxide, tin oxide, boron oxide, zirconium oxide, there after dried and baked at temperature 600 to 900°C.

EFFECT: production of alumina support, development of production methods and methods for making dehydrogenation catalyst on this support of high mechanical strength, low abrasiveness and high activity and selectivity in dehydrogenation of propane, isobutane and isopentane.

7 cl, 2 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to obtaining catalysts, particularly catalysts for dehydrogenation of paraffin hydrocarbons into olefins. Description is given of a catalyst for dehydrogenation of C3-C5-paraffin hydrocarbons into olefins, containing, in wt %: chromium (III) oxide - 8.0-23.0; alkali metal oxide - 0.5-3.5; zirconium oxide or a mixture of oxides of zirconium, hafnium and titanium with mass ratio of 1:(0.01-0.3):(0.001-0.05)-0.05-5.0; carrier - rehydrated oxygen-containing aluminium compound with general formula: Al2O3-x(OH)2x·nH2O, where x=0.1-0.5, n=0.7-1.5, with an x-ray amorphous structure, containing 10-50% pseudo boehmite.

EFFECT: increased catalytic activity and stability due to reduced loss during attrition.

5 cl, 2 tbl, 4 ex

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