The catalyst synthesis of methylmercaptan

 

(57) Abstract:

The catalyst has the following composition, wt.%: the oxide tungsten (VI) 7,0 - 12,1; alumininum potassium 6,0 - 10,0; sodium oxide and/or boron 0,3 - 3,0; aluminium oxide - rest; the aluminum oxide has a volume of transport pores with a radius of 70 - 100 nm of not less than 0.06 cm3/, the Catalyst has a high activity and retains high selectivity for methylmercaptan. 1 C.p. f-crystals, 1 table.

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

One of the ways to obtain a mercaptan is the interaction of methanol with hydrogen sulfide

CH3OH + H2S = CH3SH + H2O

The reaction is complicated by the formation of by-products, resulting in lower selectivity to metalcaptase. To reduce the output of by-products and to increase the selectivity for metalcaptase possible by conducting the process at moderate temperatures and the excess of hydrogen sulfide relative to methyl alcohol, as well as selecting appropriate catalysts. The process can be done in the presence of various catalysts.

Ka is hydrated aluminum hydroxide and other highly active, [Mashkina A. C., Paukshtis E. A., Yakovlev, C. N. Synthesis of mercaptan from methanol and hydrogen sulfide in the presence of acid catalysts. Kinetics and catalysis. 1988. So 29. S. 596; U.S. patent N 5283369, C 07 C 319-08, 1994], but to obtain mercaptan with high selectivity it is necessary to use a large excess of hydrogen sulfide to methyl alcohol, usually (4 - 5) : 1 (mol.), what complicates the technology.

The catalysts of the basic type high selectivity for methylmercaptan is achieved at a molar ratio of hydrogen sulfide to methyl alcohol (1.5 to 2) : 1. Thus, the known catalysts, representing the aluminum oxide modified with hydroxides or carbonates of alkali metals [Mashkina A. C., Kutenkov C. M. and other activity of the main catalysts in the reaction of methanol with hydrogen sulfide. Kinetics and catalysis. 1988. So 29. S. 1174; Catalytic synthesis of mercaptan from methanol and hydrogen sulfide. Kinetics and catalysis. 1992. So 339. S. 1128; patent EP N 749961, B 01 J 21/04, 1996]. In their presence there is a large output side product of dimethyl sulfide and oxides of carbon.

The most effective catalyst in the production of methylmercaptan is aluminum oxide, modified 10 - 15 wt.% the potassium tungstate. So, the world is">

The disadvantage of this catalyst is the low activity mercaptan.

Closest to the present invention is a catalyst [RF patent N 1316127, B 01 J 23/04, 1996], containing in its composition, wt.%: the potassium tungstate - 12 - 15, a boron oxide - 2 - 3.6, the oxide luminia the rest were obtained by bias or impregnation. [RF patent N 1608923, B 01 J 37/02, 1996] to obtain a catalyst of the composition must be used lumbardy carrier having a specific volume of pores with a radius greater than 100 nm 0.08 - 0.13 cm3/year For the implementation of the production of methylmercaptan high power requires a more active catalyst.

The problem solved by this invention is to increase the activity of the catalyst with high selectivity for methylmercaptan.

The problem is solved due to the fact that the catalyst contains a compound of potassium as potassium aluminate - KAlO2: compound of tungsten in the form of amorphous tungsten oxide (VI)- WO3; aluminum oxide has a volume of transport pores with a radius of 70 - 100 nm is not less than 0.06 cm3/g and contains one of the elements of the group of sodium, boron, or their mixture, and the catalyst has the following composition, wt.%: the oxide tungsten (VI) 7.0 - 12.1%; alberson, the proposed catalyst in contrast to the known is characterized by a number of significant differences:

connection of potassium in the catalyst is in the form of potassium aluminate;

connection of tungsten in the form of amorphous tungsten oxide (VI):

the aluminum oxide has a volume of transport pores with a radius of 70 - 100 nm is not less than 0.06 cm3/g and contains one of the elements of the group of sodium, boron, or a mixture thereof.

The catalyst has the following composition, wt.%: the oxide tungsten (VI) 7.0 - 12.1; potassium aluminate 6.0 - 10.0; sodium oxide and/or boron 0.3 - 3.0; aluminium oxide - rest.

The proposed set of distinctive features allows you to increase the activity of the catalyst while maintaining a high selectivity for methylmercaptan.

The catalyst is prepared by impregnation or mixing. For the preparation of the catalyst by impregnation using alumina with a surface of 300 - 350 m2/g, containing 0.07 - 0.16 wt.% sodium oxide, boron 0.4 - 3.2 wt. % or without boron. Alumina impregnated with solutions of compounds of tungsten and potassium, are heat treated. The preparation of the catalyst by the method of mixing the catalyst mixture containing aluminum hydroxide, acid, compounds of tungsten, potassium and p is illustrated by the following examples:

Example 1.

For the preparation of the catalyst is aluminum oxide with a specific surface area of 350 m2/g and containing sodium oxide, impregnated successively with aqueous solutions of compounds of tungsten and potassium and is subjected to heat treatment. The composition of the catalyst, wt. %: tungsten oxide - 7.0, potassium aluminate - 6.0, sodium oxide - 0.07, alumina - rest.

Example 2.

Similar to example 1, except that the alumina contains boron. The catalyst composition, wt.%, : tungsten - 10.6, potassium aluminate - 6.0, sodium oxide - 0.07, boron - 0.3, alumina - rest.

Example 3.

Analogous to example 2. The catalyst composition, wt.%: tungsten - 10.2, potassium aluminate - 8.3, boron - 1.24, sodium oxide - 0.135, alumina - rest.

Example 4.

Analogous to example 2. The catalyst composition, wt.%: tungsten oxide is 12.1, potassium aluminate - 10.0, boron - 3.0, sodium oxide - 0.14, alumina - rest.

Example 5.

For the preparation of the catalyst is mixed aluminum hydroxide containing sodium, boric acid and potassium compounds, and tungsten. The mixture plastificator, mold and subjected to heat treatment. The catalyst composition, wt.%: tungsten - 10.logical example 5, only use acetic acid. The catalyst composition, wt.%: tungsten - 10.6, potassium aluminate - 8.0, sodium oxide - 0.04, alumina - rest.

Example 7.

Similar to example 6. The catalyst composition, wt.%: tungsten 7.1, luminal potassium - 9.5, sodium oxide - 0.07, alumina - rest.

Examples 8 and 9 are shown for comparison.

Example 8.

Similar to example 1, except that the catalyst no tungsten. The catalyst composition, wt.%: the potassium aluminate - 9.0, sodium oxide - 0.07, alumina - rest.

Example 9.

Similar to example 1, except that the catalyst no potassium aluminate. The composition of the catalyst, wt. %: tungsten - 10.7, sodium oxide - 0.07, alumina - rest.

Distribution in the catalyst pore size determined by the method of mercury porometry on paramere 2000 company "Carlo-Erva" (Italy). Catalytic activity 4 - 6.4 mm is determined in the process of synthesis of mercaptan from methanol and hydrogen sulfide on running the installation under atmospheric pressure, a temperature of 355 - 360oC, molar ratio of H2S : CH3OH = 1.7 - 1.8 and different contact times. The contact time is determined by the ratio of the volume rolled the RA in ml/sec (P = 0.1 MPa, T = 20oC). According to the results of chromatographic analysis of the reaction products calculate the conversion of methyl alcohol in %, the yield of mercaptan, in mol.% and selectivity for methylmercaptan, equal to the ratio of the output of the mercaptan to the conversion,%. The catalyst is judged by the rate constant of formation of mercaptan, K, s-1. Performance is expressed as the moles of mercaptan formed per 1 liter of catalyst per hour.

The results of tests of catalysts at the time of contact with 8.4 shown in table. 1.

As seen from the above examples, the catalysts containing 6.0 - 10.0 wt. % potassium aluminate, 7.0 - 12.1 wt.% amorphous tungsten oxide (VI) show higher activity than the known catalysts, which are aluminum oxide promoted with potassium tungstate, while maintaining a high selectivity for methylmercaptan. Prepared according to the invention the catalyst may be boron or its content is 0.3 - 3.0 wt.%, moreover, boron is introduced into the lattice Al2O3forming a connection Al-O-B-O-Al. The active catalyst has a volume of transport pores with a radius of 70 - 100 nm is not less than 0.06 cm3/g, with less content transport then Atweet tungsten, not active as catalysts acid type containing only tungsten, discollection the mercaptan. We offer a catalyst containing separately potassium compounds and tungsten has a high activity and a high selectivity for methylmercaptan compared with the known catalysts.

As can be seen from the examples and tables offer the catalyst has high activity and selectivity and can find industrial application in the synthesis of mercaptan from methanol and hydrogen sulfide used in the synthesis of methionine and other chemical compounds.

1. Catalyst to obtain mercaptan from methanol and hydrogen sulfide, incorporating potassium compounds, tungsten, boron, aluminum oxide, characterized in that the compound of potassium is in the form of aluminate, potassium, compounds of tungsten in the form of amorphous tungsten oxide (VI), aluminum oxide contains one element from the group of sodium, boron, or their mixture and the catalyst has the following composition, wt.%:

The oxide tungsten (VI) - 7,0 - 12,1

The potassium aluminate - 6,0 - 10,0

The sodium oxide and/or boron - 0,3 - 3,0

Alumina - Rest

3. The catalyst p. 1, wherein

 

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