The way to obtain methyl chloride

 

(57) Abstract:

Use: solvent. The inventive method of obtaining methyl chloride. Reagent 1: methanol. The reagent 2 - hydrogen chloride. The synthesis conditions of 250 - 350°C, pressure 2 - 4 bar, the catalyst is active microspherical gamma alumina with an average particle size of 20 to 200 μm, in the fluidized bed, the portion of the catalyst withdrawn from the reaction zone to the regeneration zone are returned to the reaction zone. 4 C. p. F. - ly.

The invention relates to a catalytic method for producing methyl chloride by the interaction of methanol with hydrogen chloride in the gas phase and can be used in the chemical industry. This reaction is usually carried out at a temperature of 280-350aboutC, pressure up to 5 bar and a molar ratio of HCl:MeOH, equal to 0.8 to 1.5. A by-product is dimethyl ether, it is difficult separable from methyl chloride due to the closeness of the boiling points. As a catalyst can be used active-alumina. The disadvantage of the process is the rapid deactivation of the catalyst due to blocking of active surface carbon deposits.

A method of obtaining methyl chloride ot the process is performed on Corning-alumina with particle size of 3-6 mm, impregnated with metal salts. The method is carried out in a tubular reactor with a fixed catalyst bed at a temperature of 250-400aboutC, a pressure of 1 ATM and a molar ratio of HCl:MeOH equal (1,05-1,15):1. In a tubular reactor with a fixed layer of aluminum oxide with additions of KCl and MnCl2the release of methyl chloride at 1300 h decreased from 95% to 93% yield of dimethyl ether was increased from 1 to 1.4% In the same conditions covered-alumina was completely deaktivirovana for 188 h, the content of carbon deposits on the catalyst to 1.57 wt. The disadvantage of this method is the necessity of using an expensive catalyst and need periodic replacement due to the inability of regeneration. Furthermore, the method is characterized by high yield by-product.

A method of obtaining methyl chloride by the interaction of methanol with hydrogen chloride on active aluminum oxide (tiled application Germany N 1907088, class C 07 C 17/16, published 1976) [2] Use a cutting-alumina with particle size of 6.3-12,6 mm Method is carried out in a cooled tubular reactor with a fixed catalyst bed at a temperature 289-360aboutC, pressure up to 10 ATM and a molar ratio of Hcl:MeOH, R. is E. the length of operation and the method of catalyst regeneration are missing.

Closest to the proposed to the technical essence and the achieved results is a method for methyl chloride by the interaction of methanol with hydrogen chloride on active aluminum oxide (patent Germany N 3016220, class C 07 C 19/02, 1981) [3] Use granulated-alumina with particle size of 3-6 mm Method is carried out in a tubular reactor with a fixed catalyst bed, cooled by coolant with a temperature of 300-320aboutC, at pressures up to 11 MPa, and a molar ratio of HCl:MeOH equal to from 1.0 to 1.33):1. For the regeneration of the catalyst is proposed to introduce into the reaction mixture of pure oxygen in a molar ratio of ABOUT2:MeOH equal (0,002-0,114):1. In a tubular reactor in the absence of additives oxygen output methyl chloride for 117 h decreased from 94,5 to 23.5% due to formation of carbon deposits. With the introduction of a mixture of 1.3 mol. oxygen the amount of carbonaceous deposits formed during the same period, decreased in 14 times. However, when implementing this method in the absence of oxygen, the catalyst is rapidly deactivated, which requires periodic replacement. The feed to the reactor of oxygen in a mixture with methanol and hydrogen chloride at elevated pressure and temperature dramatically increases fire and warywoda to increase yield of methyl chloride and reduction of the content of dimethyl ether in the long run of the reactor, and improve the manufacturability of the way. This problem is solved in the present invention.

In a method of producing methyl chloride by the interaction of methanol with hydrogen chloride on active aluminum oxide, according to the invention, as microspherical catalyst used is aluminum oxide with an average particle size of 20-200 μm, and the process is carried out in the fluidized bed. Part-alumina can be output from the reaction zone to the regeneration zone and to return to the reaction zone.

The process in the reaction zone is preferably carried out at a temperature of 250-350aboutC, a pressure of 2-4 bar, the contact time of 20-30 s, fictitious gas velocity based on the free section of the reactor of 0.1-0.5 m/s

In the regeneration zone of oxy aluminum is subjected to oxidative treatment of oxygen-containing gas at a temperature varying between 250 and 600aboutC and a pressure of 2-4 bar. As the oxygen-containing gas, you can use the air. The average residence time of particles of aluminum oxide in the regeneration zone is 10-100 minutes

To maintain the optimum operating conditions of the catalyst, the process is carried out so that a portion of the catalyst withdrawn from the reactor in a remote regenerator with pseudoo the surface-aluminum oxide, supported within 0.6-1.2 wt. (preferably of 0.8-1.0 wt.).

To prevent the formation of carbon monoxide in the regeneration process are introduced platinum or other catalyst for additional oxidation of carbon monoxide in the number (1-100) of 10-6from the mass of catalyst in the system. Before serving on the regeneration of the catalyst is treated with an inert gas or superheated steam for desorption of reactants and reaction products. The regenerated catalyst before returning to the reactor is treated with hot nitrogen or steam in order to remove adsorbed products of oxidative regeneration.

The proposed method allows to obtain a methylene chloride with access 97-98,5% when the degree of conversion of methanol 98-99% and the content of dimethyl ether in contact with gas in the range of 0.02-0.5% Catalyst in the recommended conditions are readily regenerated. The use of a reactor with a fluidized bed of finely dispersed catalyst allows for the optimal process conditions to maintain the activity and selectivity of the catalyst is practically at a constant level, which is particularly important for installations of large capacity. The use of relatively cheap cateel, due to the entrainment of fines formed by attrition.

The proposed method differs from [3] that as microspherical catalyst used is aluminum oxide with an average particle size of 20-200 μm, and the process is carried out in the fluidized bed. Thus, the proposed method meets the criteria of the invention of "novelty."

The present invention was able to overcome the long-standing prejudice experts that it is impossible to carry out the interaction of methanol with hydrogen chloride on alumina in a fluidized bed with a high yield of the main product in the long run. Thus, the proposed method satisfies the criteria of the invention "inventive step".

The proposed method can be used in the chemical industry, by reducing the concentration of by-product chloride in the stands, to increase the service life of the catalyst is aluminum oxide, to increase the adaptability of the method by excluding fire and explosion hazard process. Thus, the proposed method satisfies the criteria of the invention "industrial applicability".

P R I m e R 1. In the reactor pseudowire is a rate of 1:1,2. The process is carried out at a temperature of layer 300aboutC, a pressure of 4 ATA, contact time 30 seconds Fictitious velocity of the gas in the calculation on the free section of the reactor is 0.2 m/s At the beginning of the path, the degree of conversion of methanol is 98,7% yield methyl chloride 98.6% of the content of dimethyl ether chloride in the stands of 0.02% After 120 h the release of methyl chloride is reduced to 94.3% of the content of the coke in the catalyst is about 1.6 wt.

P R I m m e R 2. In the reactor with a fluidized bed microspherical-aluminum oxide is a mixture of methanol vapor and hydrogen chloride. The process is carried out at the conditions in the reaction zone, as described in example 1. From the reaction zone 3 wt. -alumina per hour is displayed in a regeneration zone where carbonaceous deposits are burned away by air at 450aboutC. the Regenerated catalyst is returned to the reaction zone. The ratio of the volume of the reaction zone to the volume of the regeneration zone is 20:1. The residence time of the catalyst in the regeneration zone 100 minutes the content of the coke in the catalyst at the outlet of the reaction zone is 0.60 wt. at the outlet of the regeneration zone to 0.20 wt. The degree of conversion of methanol is 98% yield methyl chloride 97.9% of the content of dimethyl ether chloride in the stands 0,02%

aboutWith the pressure of 2 ATA, contact time 20 C. Fictitious velocity of the gas in the calculation on the free section of the reactor is 0.3 m/s From the reaction zone 5 wt. -alumina per hour is displayed in a regeneration zone where carbonaceous deposits are burned away by the gas containing about 10. oxygen at 600aboutC. the Ratio of the volume of the reaction zone to the volume of the regeneration zone is 120:1. The residence time of the catalyst in the regeneration zone 10 min. Content of coke in the catalyst at the outlet of the reaction zone is 1.20 wt. at the outlet of the regeneration zone to 0.15 wt. The degree of conversion of methanol is 96% yield methyl chloride 95.9% of the content of dimethyl ether chloride in the stands 0,01%

When carrying out processes according to the method of [3] which was the prototype of the invention, the yield of methyl chloride does not exceed 94,5% in Addition, upon receipt methyl chloride by hydrochloridebuy methanol in a tubular reactor with a fixed layer of aluminum oxide content of dimethyl ether chloride in the stands reaches 0,2-2,4 about. [2] From the above examples show that the proposed method can provide a higher yield of methyl chloride at a substantially lower content of dimethyl afio has increases its adaptability.

1. The WAY to OBTAIN METHYL CHLORIDE by the interaction of methanol with hydrogen chloride in the gas phase on active aluminum oxide at elevated temperature and pressure 2 - 4 bar with regeneration of the catalyst oxygen-containing gas, characterized in that as g-alumina used microspherical g-alumina with an average particle size of 20 to 200 μm, and the process is carried out at 250 - 350oWith in the fluidized bed, with g-alumina is removed from the reaction zone to the regeneration zone and after regeneration is again returned to the reaction zone.

2. The method according to p. 1, characterized in that the regeneration zone g-alumina is subjected to oxidative treatment of oxygen-containing gas at a temperature of 450 - 600oAnd pressure 2 - 4 bar.

3. The method according to p. 2, characterized in that as the oxygen-containing gas using the air.

4. The method according to PP.1 to 3, characterized in that the average residence time of the particles g of aluminum oxide in the regeneration zone is 10 to 100 minutes

5. The method according to PP. 1 to 4, characterized in that the process in the reaction zone is carried out at contact time of 20 to 30 C.

 

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