NL8201123A - METHOD FOR PREPARING CHLORINE ALKANES. - Google Patents

Description

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Process for preparing chloroalkanes.

The invention relates to a process for the selective production of chloroalkanes by chlorination of alkyl chlorides.

Chloroalkanes are prepared industrially by direct gas phase chlorination of the corresponding alkane and / or alkyl chloride. For example, methane can be chlorinated in the gas phase to form a mixture of chloromethanes, namely methyl chloride, methylene dichloride, chloroform and carbon tetrachloride. On the other hand, methyl chloride, preferably obtained by the direct hydrochlorination of methanol in either the gas or liquid phase, can be further chlorinated in the gas phase to the three heavier chloromethanes, and, if desired, the hydrogen chloride produced in the chlorination reaction can be recycled for reaction with methanol. The aforementioned chlorination processes for the production of chloromethanes are described, for example, in the following general references: "Chloromethanes" EM Forrest Encyclopedia of Chemical Processing and Design, Vol. 8, pp.211-270, 1979 and in "Chloromethanes" Kirk-Othmer Encyclopedia of Chemical Technology 20 3rd Edition, Volume 5 pp. 677-711979.

The demand for specific chloroalkanes varies from time to time and it is desirable to have a process capable of obtaining a large control of product selectivity with respect to the chloroalkanes obtained from a particular alkyl chloride. A catalytic process has now been found which is particularly effective for the selective production of methylene chloride from methyl chloride.

8201123 «* -2-

According to the invention there is provided a process for the selective production of chloroalkanes in which an alkyl chloride and chlorine in the vapor phase are contacted at an elevated temperature in the presence of a catalyst containing a zeolite.

A wide variety of zeolites can be used as catalysts, provided they are stable or chlorination conditions. Suitable zeolites include X type zeolites (for example, as described in British Patent 1.1 * 50.1 * 11; U.S. Patent 2,882.21 * 1;), Y type zeolites (for example, as described in U.S. Patent 3,130,007 ) and zeolite Nu-2 (as described in related British patent application 8.01 * 0.782).

The zeolite catalysts are preferably exchanged in whole or in part with metal cations, for example one or more copper, silver, magnesium, zinc, manganese, cobalt, nickel and lanthanide cations. The preferred catalysts consist of zeolites which have been partially or wholly exchanged with silver and / or manganese cations, most preferably silver and manganese cations. It will be appreciated that during the chlorination the above-mentioned metal cations, which may be present as metals or metal compounds eg oxides, can be converted in whole or in part under the reaction conditions into chlorides during the course of the reaction.

The catalyst can be used in suitable, fixed, moving or fluidized beds.

The process of the invention applies to a wide variety of alkyl chloride starting materials, for example, alkyl chlorides with 1 - U carbon atoms. The method is particularly applicable to the selective production of methylene dichloride from methyl chloride.

The reaction temperature may vary according to the alkyl halide reagent used. For the chlorination of methyl chloride or ethyl chloride, for example, it is suitable to use a temperature in the range of 275-500 ° C and preferably between 300-500 ° C, for example 350-150 ° C.

8201123 -3- ί *

The reaction is usually carried out under atmospheric or superatmospheric pressure, for example at a pressure in the range of 0.1-10 MPa.

The process is preferably carried out in the presence of a source of molecular oxygen, eg oxygen itself or oxygen-enriched air, since this minimizes coking problems, contributes to zeolite stability and is essential for the HCl utilization through the Deacon reaction. The presence of oxygen is also effective to improve the ratio of methylene chloride to chloroform and carbon tetrachloride for a given degree of conversion. However, suitable chlorination will take place in the presence of oxygen. An inert diluent such as nitrogen can also be present.

The molar ratios of alkyl chloride to chlorine are suitably in a range from 10: 1 to 1:10, for example 2: 1.

The molar ratios of alkyl chloride to oxygen (if any) are suitably in a range from 100: 1 to 1: 1, for example, 2: 1.

The reaction products may be isolated and used as such or, if desired, recirculate in whole or in part to the chlorination reaction to increase the yield of specific chloroalkanes.

The invention is illustrated by the following examples.

Example 1

A Y-type zeolite of the formula NagO.AlgO ^. Is saturated. SiOg with 10 ml of 50 $ s ΜηίΝΟ ^^. Β HgO solution 30 for 16 hours and then filter and wash thoroughly with water.

The white solid is then treated with 10 ml of 80% silver nitrate solution for 16 hours, filtered, washed, dried at 120 ° C for 16 hours and then calcined at 50 ° C. The resulting catalyst was found to contain 18.9 silver and 2.1: 35 manganese in analysis. After grinding to a screen size of 0.590-0.81: 0 mm, the catalyst is packed as a 10 cm bed into a 82.0 1 1 23 4 microreactor tube with an outer diameter of 6.3 mm, surrounded by a resistance heated oven and connected to a GLC system incorporated in the production line. After treatment in running chlorine at 1 ° C ° C, catalyst tested with methyl chloride over a range of gas feed compositions and temperatures. The results are shown in Table 1.

A comparative example is performed at 40 ° C, replacing the silver / manganese / zeolite catalyst with an equal amount of pumice ground to the same screen size. The results are shown in Table 2. A comparison of these results with those shown in Table 1 illustrates the greater selectivity to methylene dichloride using the silver / manganese / zeolite catalysts.

Example 2 The Y-type zeolite of Example 1 is also tested without cation exchange and also appears to have a favorable behavior with regard to the use of pumice alone. The results are shown in Table 3.

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Example 3

A catalyst containing silver, manganese and magnesium as in Example 1 is prepared, exchanging a Y-type zeolite with an aqueous solution of the 8 H ml 5 50 $ manganese nitrate solution, 2.6 g of magnesium nitrate in 5 nil. water and 1.7 g of silver nitrate in 5 ml of water. After calcination and pretreatment with chlorine, the catalyst is tested under various conditions of gas supply and temperature.

The results are shown in Table 10. The results obtained in the presence of nitrogen diluent rather than air are shown in Table 5 along with those of the blank (pumice) reaction under such conditions.

Example U

A catalyst as in Example 2 is prepared, but yttrium is substituted for magnesium. 3.1 g of the zeolite is exchanged with a solution containing 3 g of yttrium nitrate and 1.33 g of silver nitrate in 10 ml of water and 6.6 ml of a 50% solution of manganese nitrate.

The results obtained with a 10 cm bed length and flow rates of U ml / min of methyl chloride and chlorine and 10 ml / min of air are shown in Table 6.

Example 5

A catalyst as in Example 1 is prepared, but 25 are tested in a 1 meter bed length reactor and the performance is compared with the same bed length on pumice stone. The reaction temperature is 280 ° C, the feed composition 20 vol. Methyl chloride with nitrogen as the sole diluent. The chlorine concentration is allowed to vary to vary the conversion rate per throughput. The decreased amounts of CHCl2 and CCl2 produced in the effluent from the catalyst with respect to that of pumice are illustrated in Table 7.820 1 1 23 -9-

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Claims (6)

1. Process for the selective production of chloroalkanes, characterized in that an alkyl chloride and chlorine in the vapor phase are contacted at an elevated temperature in the presence of a catalyst comprising a zeolite. 2. Process according to claim 1, characterized in that methyl chloride is reacted with chlorine to form methylene chloride. Process according to claim 1 or 2, characterized in that the catalyst consists of a zeolite which has been exchanged in whole or in part with one or more copper, silver, magnesium, zinc, manganese, cobalt, nickel and lanthanide cations. Process according to claim 3, characterized in that the catalyst consists of a zeolite, which is wholly or partly exchanged with silver and / or magnesium cations. Process according to any one of the preceding claims, characterized in that the reaction temperature is in the range of 300-500 ° C. 6. Process according to any one of the preceding claims, characterized in that the reaction is carried out in the presence of a source of molecular oxygen. 7. Process according to claim 6, characterized in that a molar ratio of alkyl chloride to oxygen is used in a range from 100: 1 to 1: 1. Process according to any one of the preceding claims, characterized in that a molar ratio of alkyl chloride to chlorine is used in a range from 10: 1 to 1:10. Method according to claim 1, substantially as described above with reference to the preceding examples. (8201123