A method of producing a catalyst for the synthesis of methylmercaptan and dimethyl sulfide

 

(57) Abstract:

Use: petrochemical industry, in particular the production of catalysts for the synthesis of methylmercaptan and dimethylsulfide. The inventive catalyst is prepared by impregnation lumbridge media the pore radius of 100 nm and a specific volume of 0.8 to 0.13 cm3/g with a solution of potassium tungstate. The impregnated carrier is calcined in a preheated oven at 380 - 500oC. the Catalyst contains a 7.5 -10 wt.% the potassium tungstate. table 1.

The invention relates to improved methods for producing mercaptan with a high content of dimethyl sulfide and can be used in the production of methylmercaptan, and in the process of production of dimethyl sulfide.

Known alumina carrier, structural and mechanical properties which regulate boron compounds and further heat treatment [1]

However, the resulting lumbardy media does not provide simultaneously high yield of mercaptan and dimethyl sulfide.

A method of obtaining methylmercaptan, selected as a prototype, in which to obtain the activated catalyst is used, the oxide aluminia use the sulfides of the metals or salts and oxides of potassium, for example, a carbonate or potassium tungstate in an amount of 10 wt. [2]

However, the catalyst also does not provide simultaneously high yield of mercaptan and dimethyl sulfide.

The aim of the invention is to increase the yield of dimethyl sulphide in the process of obtaining mercaptan using a catalyst containing potassium tungstate.

The objective is achieved by the fact that the use of catalyst for the synthesis of mercaptan from methanol and hydrogen sulfide by impregnation lumbridge media the pore radius of 100 nm, a volume of 0.08 to 0.13 cm3/g solution wolframate potassium content in the finished catalyst 7.5 to 10 wt. with subsequent annealing in a preheated oven at 380-500aboutC.

As a carrier, it is preferable to use boron aluminum oxide, obtained by the method of thermo-mechanical activation.

Thus, the proposed method in contrast to the known is characterized by a number of significant differences in the production technology: the use of media with the pore radius of 100 nm, a volume of 0.8 to 0.13 cm3/g; application of potassium tungstate in the amount of 7.5 to 10 wt. subsequent calcination of the catalyst Les stage of deposition of the active component is immediately stage heat treatment at t 380-500aboutWith, without stages of wilting and drying.

The method is as follows.

The aluminum oxide containing2ABOUT3the number 2-3,6 wt. and the volume of macropores with r > 100 nm 0.08 to 0.13 cm3/y capacity is sprayed through nozzles aqueous solution of potassium tungstate to the content of potassium tungstate in the finished catalyst 7.5 to 10 wt.

The obtained semi-finished product without wilting in the air and drying in a drying Cabinet is placed immediately for 2-4 h in a pre-heated up to t 380-500aboutWith oven.

Test the activity of the catalysts in the reaction between hydrogen sulfide and methane to form LCA was performed in a flow-through setup with 380aboutC and a molar ratio of H2S:CH3HE _1,8.

Analysis of the initial mixture and the composition of the gas after contact with the catalyst is carried out chromatographically.

The distribution of the pore radii were determined by the method of mercury porometry on paramere 2000 company "Sarlo rba" (Italy).

P R I m e R 1 (the prototype). To 91 g of aluminum oxide with a specific surface area of 230 m2/g add a solution of potassium tungstate, with a content of 10 wt. in the finished catalyst. The catalyst was dried, calcined. Content is and 1.7 mol

P R I m m e R 2. To 91 g of aluminum oxide containing 3.6% B2ABOUT3and the specific volume of the macropores of 0.08 cm3/y capacity spray impregnating solution containing 8 g of potassium tungstate in 71 ml of water with a speed of 0.3 l/h per 100 g of catalyst.

Next, the catalyst mass is placed in an oven, preheated to 380aboutC, and incubated for 4 h

The content of H2WO4in the catalyst 8 wt.

The output of methylmercaptan 65 mol%

The yield of dimethyl sulfide 14 mol%

P R I m e R 3. Similar to example 2, only the volume of pores with r > 100 nm is equal to 0.13 cm3/, Content K2WO4in the catalyst 8 wt.

P R I m e R 4. Similar to example 2, only the content of potassium tungstate in the finished catalyst is 7.5 wt.

P R I m e R 5. Similar to example 2, only the content of the K2WO4in the catalyst is 6 wt.

P R I m e R 6. Similar to example 2, only the content of the K2WO4in the finished catalyst 13 wt.

P R I m e R 7. Similar to example 2, the temperature of calcination is equal to 330aboutC.

P R I m e R 8. Similar to example 2, the temperature of calcination is 500aboutAnd the content of the active components is in the catalyst 8% present stage of wilting on the air 6 h, stage of drying at t 120aboutWith 4 hours.

P R I m e R 10. Similar to example 2, the temperature of calcination 600aboutC.

P R I m e R 11. Similar to example 2, only the volume of pores with r > 100 nm 0.05 cm3/,

P R I m e R 12. Similar to example 2, only the volume of pores with r > 100 nm of 0.15 cm3/,

Examples describing the proposed method, shown in the table.

Using the presented method of preparation of the catalyst was possible to obtain a high yield of mercaptan (65 mol.) and at the same time dimethyldisulfide (11,5 14 mol.).

As can be seen from examples 2,3,4 and 8, the use of boron oxide with aluminum pores radius r > 100 nm, a pore volume of 0.08 to 0.13 cm3/g and the content of potassium tungstate in the finished catalyst 8-10 wt. leads to increase in the yield of dimethyl sulfide.

When increasing the volume of pores with r > 100 nm more of 0.13 cm3/g (example 12) loss of strength of the catalyst for reducing the volume of pores with r > 100 nm less than 0.08 cm3/g (example 11) decreases the yield of mercaptan and dimethyl sulfide.

The concentration of potassium tungstate in the finished catalyst is 7.5-10 wt.

The decrease in the number of K2WO4< 7.5 m WO4> 10 wt. (example 6) decreases the yield of dimethyl sulfide and the goal is not reached.

It can be assumed that the decrease in the content of potassium tungstate leads to the release of acidic centers, stimulating the reaction of dimethyl sulfide.

The obtained catalyst mass immediately after impregnation placed in a preheated furnace (t 380-500aboutC), resulting in a catalyst, in the presence of the release of dimethyl sulfide equal 11-14 mol% while maintaining a high yield of mercaptan.

With increasing temperature of annealing above 500about(Example 10) output dimethyl sulfide falls.

If under the same conditions of preparation of the active catalyst additionally carry out the stage of wilting and drying at t 120about(Example 9) output dimethyl sulfide is reduced to 4.5 mol.

An increase in the yield of dimethyl sulfide, apparently related to the amount and distribution of the active ingredient by volume of the granules of the catalyst.

Thus, using the proposed method provides compared to prototype the advantage of increasing the yield of dimethyl sulfide while maintaining a high yield of mercaptan.

3/g and the impregnation is carried out until the content of potassium tungstate in the finished catalyst 7.5 to 10.0 wt. % followed by annealing in a preheated oven at 380 - 500oC.

 

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