DE1593715B - Process for the oxychlorination of olefins and chloroolefins - Google Patents

Description

The procedure can take place at relatively low

Temperatures are carried out. In general, temperatures of around 220 ° C are sufficient, however, a reaction temperature of

It is known that 1,2-dichloroethane can be used from 240 to 260 ° C.

put that you can ethylene with hydrogen chloride and usually the reaction is in a fixed bed

Oxygen or air carried out in the presence of copper chloride, _a5. It is also possible, in Wirbelbei about 250 to 300 ° C brings (see for reaction. _Sc hichtverfahren to work. In this case, German Patent 430 539 and Chemical engi- can inert carrier be _{dispensed d} i _e use, neenng Progress 46 , Pp. 483 to 485). _{It is} surprising that this is part of the graphite

_Is the formation of hot zones, a major difficulty, _layered copper chloride as the Deacon contact effective in Gasphasenoxychlorierung in the presence _{3o and} drigen _{at n} i _e reaction temperatures produce a Deacon contact occurs. Do you work z. B. _rage walls yields. Also, with fixed catalytic converters, so form
in the reaction space highly overheated zones with temperatures of 700 to 800 ° C. This results in undesirable higher chlorinated compounds, and the ₃₅
Hydrocarbon is degrading

by incorporating copper chloride in the graphite lattice, its volatility is greatly reduced.

Yield partially burned. In addition, the contact is made by sublimation of Copper chloride ineffective.

In order to achieve a uniform temperature distribution in the _water- free contact space, the contact was
arranged in the fluidized bed (cf. USA.-Patent
2,644,846 and French patent specification 918,985). In
in this case, the supplied hydrogen chloride is

example 1

Production of the copper (II) chloride graphite intercalation compound and oxychlorination

Flake graphite is intimately mixed with 25 percent by weight copper (II) chloride. This mixture is kept for 8 days in an electrically heated tube in the presence of a weak stream of chlorine heated to 400 ° C. After the copper (II) chloride has been installed in the graphite lattice, the

not fully implemented. In addition, the con- strongly dusty ₄₅ intercalation compound as a fluffy black Pultakt by abrasion of the contact carrier. _{ver vor The} catalyst produced in this way is with Man has also tried to make the formation superheated

id ß d

To prevent reaction zones by the fact that the catalyst by admixing non-impregnated inert carrier material, in particular silicon carbide, diluted (see German Auslegeschrift 1 047 760). With such an arrangement, however, a large part of the available reaction space is possible lost.

In a further process, the heat released by adding graphite to the heat-dissipating reaction wall are passed. In order to achieve the desired effect, a reactor must be used can be used, which consists of a variety of raw materials

ren with a small diameter.

There has now been a process for the oxychlorination of olefins and chloroolefins, by catalytic Implementation of these compounds with hydrogen chloride

and oxygen or air found, which thereby __

is characterized in that the catalyst used is copper ₆₅ and "7u" 2Vo "" from "Veninremigu7g" en '~ (Etnyichrorid, "(II) -chloride-graphite intercalation compounds 1,1,2-trichloroethane and traces of vinyl chloride) applies, the degree of conversion, based on hydrogen chloride, produced in a manner known per se, are beworden, carries 96.5%.

y-aluminum oxide mixed in a ratio of 1: 1. From it tablets with a diameter of 2 to 5 mm are pressed.

A vertical, cylindrical, 150 cm long iron pipe (inner diameter 24 mm), whose The upper and lower part is heated separately, is filled with the contact made in this way. The contact volume is 650 ml. A gas mixture of 11.21 ethylene and 21.3 liters of hydrogen chloride is sent and 61.61 air (10% excess) through the filled Reactor that is heated with circulating oil. The temperature of the circulating oil is set so that that in the upper part of the tube a reaction temperature of 240 ° C, in the lower part of the Rohres a temperature of 260 ° C is maintained. The resulting vapors are when leaving of the reactor condenses. The resulting reaction product consists of 98% 1,2-dichloroethane

Example 2

It is worked under the same conditions as in Example 1, with a instead of the iron pipe Titanium tube is used. The following results are achieved: The resulting reaction product consists of 98.9% 1,2-dichloroethane and 1.1% impurities (ethyl chloride, 1,1,2-trichloroethane, vinyl chloride). The degree of conversion, based on hydrogen chloride, is 97.5%

Example 3

As described in Example 1, a graphite-copper (n) chloride contact is used made with 50% copper (II) chloride content and with 25% y-aluminum oxide mixed. The same reaction conditions as in Example 1 are used. The Resulting reaction product consists of 98.7% 1,2-dichloroethane and 1.3% impurities (Ethyl chloride, 1,1,2-trichloroethane, vinyl chloride). The degree of conversion, based on hydrogen chloride, is 98.5%.

Example 4

The same conditions as in Example 1 are used, 11.2 l / h of vinyl chloride being used will.

The resulting reaction mixture consists of 97% 1,1,2-trichloroethane + cis-dichloroethylene and 3% from impurities (vinylidene chloride, trichlorethylene, Perchlorethylene, sym. Tetrachloroethane). The degree of conversion, based on hydrogen chloride, is 97%.

Example 5

It is carried out under the same conditions as in Example 1, with 0.5 mol / h of trichlorethylene len come to use.

The resulting reaction mixture consists of 98%

sym. tetrachloroethane and 2% impurities (trichlorethylene, perchlorethylene, pentachloroethane).

The degree of conversion, based on hydrogen chloride, is 99%.

Example 6

The same conditions as in Example 1 are used, 0.5 mol / h of trichlorethylene be applied.

The resulting reaction mixture consists of

99.5% pentachloroethane and perchlorethylene and 0.5% impurities (hexachloroethane, sym.

Tetrachloroethane). The degree of conversion, based on hydrogen chloride, is 98%.

Claims (2)

Claims: As is well known, anhydrous copper (II) chloride can be incorporated into the graphite lattice at temperatures of 400 ° C in a stream of chlorine up to a maximum content of 69.6% copper (II) chloride (cf. Angew. 5 Chem. 75 , Pp. 130 to 136 [1963]). When carrying out the oxychlorination, however, it has been shown that it is not absolutely necessary to use a contact material which has this maximum proportion of copper (II) chloride. In general is 1. Process for the oxychlorination of olefins
and chlorolefins, by catalytic conversion
these compounds with hydrogen chloride and
Oxygen or air, characterized in that the catalyst used is copper (II) chloride-graphite intercalation compounds which have been produced in a manner known per se in a ratio of copper (II) chloride to graphite. the storage connection from 25:75 to 60:40 2. The method according to claim 1, thereby sufficient. But it can also be indicated with a lower one that graphite intercalation proportion of copper (II) chloride are worked, bonds are used in which the weight ratio of copper (II) chloride to graphite has also been found to be useful 15 when inert carriers, for example kieselguhr, silica gel or 25:75 to 60:40. _r aluminum oxide, the graphite copper (II) chloride Compound are added, creating an easily deformable mixture.