DE1768493B2 - Process for the continuous production of 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane in addition to 1,2-dichloroethane by oxychlorination of ethylene - Google Patents

Description

zone from 250 to 400 ° C and in the second 35 chloroethane and 1,1,2,2-tetrachloroethane, because the prak catalyst zone of 255 to 410 ⁰ C adheres to table no 1,2-dichloroethane is present. In the on the

hottest areas following catalyst zones is the concentration of the reactants 1,2-dichloroethane, Hydrogen chloride and oxygen increased, but the temperature quite low, and the formation of 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane only takes place because of the high activation energies slow. In addition, the catalysts commonly used in the oxychlorination of ethylene

e) 0.5 to 12MoI ethylene per hour and liter 35 lysatoren a reaction which essentially leads to Catalyst feeds. 1,2-dichloroethane leads.

2. The method according to claim 1, characterized in that in the preceding claims, That one the oxychlorination shown in the invention now relates to a new process one or more tubular or vielroh- for oxychlorination of ethylene, with the opposite Devices carries out and the second 40 set to the previous process chlorinated, saturated Catalyst zoiie arranged in tubes, their compounds with 2 carbon atoms, in particular The diameter is larger than that of the tubes, which in addition to 1,2-dichloroethane, substantial proportions of 1,1,2-die contain first catalyst zone. Tetrachloroethane can be obtained, e.g. B. at least

3. The method according to claim 1 or 2, characterized in 8 mol percent, preferably 10 to 15 mol percent characterized that in the second zone 45 and up to 20 mol percent, based on the surrounding

"■ '" - converted ethylene. 1,1,2-trichloroethane and 1,1,2,2-

Tetrachloroethane are technically important products that can be used as such or as a starting material for manufac- turing

fish surface and a pore size also used between 0.05 and 10 μπι,
b) a temperature in the first catalyst

and the temperature of the hottest areas of the second zone to around 5 to 50 ° C sets a value above the temperature of the hottest areas of the first zone,

c) a molar ratio of hydrogen chloride to ethylene of 1.8 to 3.0: 1,

d) maintains a molar ratio of oxygen to ethylene of 0.5 to 1.5: 1 and

position of vinylidene chloride, dichloroethylenes and

a catalyst with greater activity than in the first zone is used.

4. The method according to claim 1 to 3, characterized in that in the second catalyst

tator zone a proportion of ethylene, hydrogen chloride 50 trichlorethylene use,

and / or containing molecular oxygen According to one embodiment of the invention

Introduces gas, with this proportion up to 60 mol.

percent of the total amount of the Reak-shaped or multi-tube device (s) used,

tion participants can be. the second catalyst zone being arranged in tubes

5. The method according to claim 1 to 4, characterized in that 55 is arranged, the diameter of which is greater than that of characterized by having a molar ratio of tubes containing the first catalyst zone; overall HCl fed in to HCl used is preferably the ratio of the diameter of these Ethylene complies with 2.10 to 2.50. Pipes> 1 and <Ξ3.

6. The method according to claim 1 to 5, characterized in accordance with another embodiment of the characterized, that one driving a molar ratio of 60 becomes a catalyst in the second zone total oxygen fed in to be used, the activity of which is higher than that of the

tem ethylene of 0.6 to 0.8.

It is well known that oxychlorination . Ethylene leads to 1,2-dichloroethane in the presence of an appropriate solid catalyst. Included

First zone catalyst.

In the present description, the term “mean specific surface” is used in the sense of the agreement used that when looking at catalyst samples at different locations on the catalyst bed removes to the specific surface of the carrier according to the method of B. E. T. (see. Uli-

3 O 4

____ Encyclopedia of Technical Chemistry Volume following catalyst zones the same or different

2/1, 3rd edition, S ^ 758) to determine the measurement results. Those used in the present process

oisse are scattered without, however, essentially consisting of the most catalytic components

apart measured values more than 100 /, from at least one compound of the following EI-

Mean are removed. _{5 ments:} ^&&

The grain size of the catalyst is in all-alkali metals, alkaline earth metals, bismuth, cad common 1 to 15 mm. It can be advantageous to use insium, chromium, cobalt, copper, tin, iron, magne- es, especially if the diameters of the tubes of the sodium, manganese, nickel, platinum, rare earth, thoden zones are close to one another or are the same , Vanadium, zinc, zirconium
A finer grain should be used in the second zone. The following examples serve to illustrate the point in the first zone, although the core size of the various embodiments does not fall below 1 mm. proper procedure

According to a preferred embodiment of the

In the process , the reactants are ethylene, Example 1

Hydrogen chloride and molecular oxygen contained i ₅ As the first reaction zone served with a 2,741 cata-

tending gas at a temperature between 280 and lyser-charged nickel tube of diameter

370 ° C passed through the first catalyst zone and 32 mm and the length 3700 mm. The catalyst

then the gas flowing out of this first zone consisted of alumina spheres with a diameter of 3 to

introduced into the second zone, the temperature of which is reduced to 5 mm, which has a mean specific surface area of

a value between 285 and 400 ° C is set, 20 1 nWg and a pore size of 0.2 to 8 μΐη on-

being the temperature of the hottest areas of the meadows and with 5 weight percent copper in the form

second zone is kept at a value around CuCl, · 2 Η., Ο and with 3 weight percent potassium

5 to 50 ° C above the temperature of the hottest were impregnated in the form of KCl.

Areas of the first zone. A tube from one was used as the second reaction zone

According to a particularly advantageous implementation 25 nickel alloy with 73 percent by weight Ni of the form, the oxychlorination is under a diameter of 65 mm, over a length of pressure from 1 to 10 bar, preferably from 2 to 7 bar, 3500 mm with alumina balls from 3 to absolutely carried out. Preferably, the second 6 mm was charged, which had a mean specific catalyst zone under a pressure above atmospheric surface area of 2 m ² / g and a pore size of 0.1, since this had the formation of 30 to 1 μτη and with 5 percent by weight of copper 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane in the form of CuCl ₀ -2 H., 0 and with 3 weight percent is favored. However, in some cases it can be impregnated with a cent of potassium in the form of KCl.
parameters other than the pressure are varied. The two reaction tubes arranged in series were the same pressure in the first catalyst zone with a gas mixture of ethylene, chlorine prevailed as in the second catalyst zone. 35 charged with hydrogen and air. The total amount of

There are preferably 2 to y mol of ethylene per fed ethylene was 2.1 mol per hour and

Hour and liter of catalyst fed in. Liters of catalyst.

According to another embodiment of the The molar ratios of the fed reaction

When driving , the operating conditions will be like this

represents that in the first catalyst zone no more 40, - «,,, _{u n} , -, _ri ™, ^ ττ ο ™

than 40 to 80% of the ethylene used, OJC ₂ U, = 0.65 and HClZC ₂ H ₁ = 2.30.

to be changed. This is z. B. causes the pressure of the reactants on entry

one in the second catalyst zone a proportion of in the first zone was 1.5 bar and on entry into

one or more of the reactants ethyl the second reaction zone 1.2 bar.

len, hydrogen chloride and / or molecular acid 45 The two reactors were double

Introduces substance- containing gas, this portion surrounding the jacket, in which a flowable medium as

up to 60 mole percent of the total amount of the heat exchanger (s) circulated and heated until

Reaction participants can be. But you can start the reaction.

cloth in which the temperature in the region of the first zone heißesten control the degree of conversion of ethylene by simultaneously the input 50 the first reactor was 350 ° to 360 ° C; the temperature feed rates of the reactants into the first door in the hottest area of the second reactor was zone and the reaction temperature of this zone was 385 to 395 ° C.
the corresponding values are fixed. For the conversion were at the exit of the

The molar ratio of the total first reaction zone fed in achieves the following results:

HCl to the C ₂ H _{4 used} is preferably between 55 _{Eth Ien a total of} 78.0%

see 2.1 and 2.5: 1; the molar ratio of total _to i. ₂ . _D ichloräthan (Xa) .... 76.3%

including the fed-in O ₂ ZC ₂ H ₄ is preferably between _ethylene ^ _{1) 2} . _T richloräthan (Xb) .. 1.0%

see 0.6 and 0.8: 1. Ethylene to 1,1,2,2-tetrachloroethane (Xc) 0.1%

The appropriate catalyst support consists of ethylene to dichloroethylenes 0.1%

from one or more substances, e.g. B. from silica 60 ethylene to vinyl chloride 0.2%

earth, silicates, clays, silicoaluminates, magnesia, ethylene to various others

Graphite and preferably made of alumina. Connections 0.3%

Very good results have been achieved with an alumina
Achieved catalyst support , the mean specific yield of 1,2-dichloroethane, 1,1,2-trichloro surface in the first zone <1 m ² / g and in the 65 ethane and 1,1,2,2-tetrachloroethane was 77.4%, second catalyst zone was <4m ² / g. based on the ethylene used.

The catalyst itself, that is to say the catalytically active component, can be in the two superimposed - (Xb -f Xc) / (Xa + Xb + Xc) = 1.4: 100.

At the exit of the second reaction zone, the conversion was complete

Total ethylene 99.5%

89.7% total HCl

Ethylene to 1,2-dichloroethane (Xa) 86%

Ethylene to 1,1,2-trichloroethane (Xb) .. 9.0 vol

Ethylene to 1,1,2,2-tetrachloroethane (Xc) 0.9 vol

Ethylene to dichloroethylenes 0.5%

Ethylene to vinyl chloride 2.2 vol

Ethylene to various others

Connections 0.5 Vo

(CO and CO ₂ 0.4Vo)

The yield of 1,2-dichloroethane, 1,1,2-trichloro Ethane and 1,1,2,2-tetrachloroethane amounted to 95.9 Vo, based on the ethylene used.

(Xb + Xc) Z (Xa -f Xb + Xc) = 10.1: 100.
Vei similar attempts

20th

It was worked as in example 1 with the following changes:

a) The catalyst in the first reactor consisted of alumina spheres with a diameter of 3 to 5 mm with an average specific surface area of 3.5 m ² / g and a pore size of 0.1 to 2 μm, which contained 5 percent by weight of copper in the form of CuCl ₂ -2 H ₂ O and were impregnated with 3 weight percent potassium in the form of KCl.

The temperature of the flowable heat exchanger became very slow until the onset of the Increased response. From that moment on, a hot spot developed, its temperature very quickly rise and became uncontrollable.

Although the temperature of the flowable heat exchanger was quickly lowered to 200 ° C, reached and then the temperature of the hot spot exceeded 550 ° C.

The analyzes of the escaping gases showed a conversion of ethylene to CO and CO ₂ over 15 Vo as a result of the combustion of the ethylene.

The further feed had to be interrupted immediately for safety reasons, but without this the temperature of the hot point could be stabilized.

b) The catalyst in the second reactor consisted of alumina spheres with a diameter of 3 to 6 mm, an average specific surface area of 0.6 m ^s / g and a pore size of 0.5 to 10 μm, with 5 percent by weight of copper in the form of CuCl ₂ · 2 H ₂ O and was impregnated with 3 weight percent potassium in the form of KCl. The catalyst of the first reactor was the same as in Example 1.

The hot zone temperatures in the first and second reactors were 360 and 370 bis, respectively 380 ° C.

The conversion results were as follows:

60

Ethylene in total 99 Vo

HCl total 86.2 vol

Ethylene to 1,2-dichloroethane 97 Vo

Ethylene to 1,1,2-trichloroethane 1.5 vol

Ethylene to 1,1,2,2-tetrachloroethane .. 0.1Vo

Ethylene to vinyl chloride 0.4 vol

Ethylene to various others

Connections <0.1%

The yields of 1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane was 98.6 Vo, based on the ethylene; the ratio (Xb -f- Xc) / (Xa + Xb + Xc) was only 1.7: 100. This shows that 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane in contrast to the aim of the invention was only obtained in very small proportions.

c) ~ The same conditions were used as in Example 1 with the exception that the The temperature of the hot area in the second reactor was brought to 445 to 455 ° C.

The conversion results were as follows:

Total ethylene 96%

Total HCl 79.6%

Ethylene to 1,2-dichloroethane 49Vo

Ethylene to 1,1,2-trichloroethane 13 vol

Ethylene to 1,1,2,2-tetrachloroethane .... 0.5%

Ethylene to vinyl chloride 21%

Ethylene to CO and CO ₂ 1 Vo

Ethylene to various others

Connections 1%

Although the ratio (Xb + Xc) / (Xa + Xb + Xc) in this case was 21.6: 100, which is quite good was high, the conversion of ethylene to 1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane only 62.5 Vo.

d) The same conditions as in Example 1 were used, with the modification that the ratio of HCl fed in to C ₂ H _{4 was} reduced to a value of 1.78.

The temperature in the hot area of the second reactor was 380 to 390 ° C.

The conversion results were as follows:

Ethylene in total 88.4 vol

HCl total 99.3 vol

Ethylene to 1,2-dichloroethane 82.5 vol

Ethylene to 1,1,2-trichloroethane 2 _S 5 vol

Ethylene to 1,1,2,2-tetrachloroethane .... 0.1 vol

Ethylene to vinyl chloride 2.5%

Ethylene to various others

Connections 0.8 Vo

The yield of 1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane was at 85.1 Vo, based on the ethylene, relatively low, as was the ratio (Xb + Xc) / (Xa + Xb + Xc) which was only 3.1: 100.

Example 2

The experimental conditions of Example 1 were modified so that in the second reactor 32 mole percent of the total amount of air was introduced immediately. The results were like follows:

Conversion at the exit of the first reaction zone:

Ethylene in total 70.1 vol

Ethylene to 1,2-dichloroethane (Xa) .... 68.7%

Ethylene to 1,1,2-trichloroethane (Xb) .. 0.8Vo

Ethylene to 1,1,2,2-tetrachloroethane (Xc) 0.1 vol

Ethylene to dichloroethylenes 0.1%

Ethylene to vinyl chloride 0.1%

Ethylene to various others

Connections 0.3%

The yield of 1,2-dichloroethane, 1,1,2-trichloro The three reactants ethylene, air and

Ethane and 1,1,2,2-tetrachloroethane was only 69.6%, hydrogen chloride were before entering the based on the ethylene used. first reactor mixed together. The gas-

(Xb + Xc) / (Xa + Xb + Xc) = 1.3: 100. S ^emic ™ "* 1 ™ ^{the most re} . ^{Actuator at a tem} "

5 temperature of 150 ° C and under a pressure on the implementation at the outlet the second reaction path of the reactor is fed in at an absolute pressure of 4.3 bar; zone: the pressure at the inlet of the second reactor was

4 bar.

Total ethylene 99.5%> The total amount of ethylene fed in was

HCl a total of 92.7 ° / om 2.3 mol per hour and liter of catalyst. The molar ethylene to 1,2-dichloroethane (Xa) ... 80.3% ratios were HC1 / C ₂ H ₄ = 2.30 and O ₂ / C ₂ H ₄ ethylene to 1,1,2-trichloroethane (Xb) .. 12% = 0.60.

Ethylene to 1,1,2,2-tetrachloroethane (Xc) 2.7 ° / · As soon as the operating stage was reached,

Ethylene to vinyl chloride 2.1%, a hot area was observed in both reactors.

Ethylene to dichloroethylenes 1.7%> 15 pays attention to its temperature in the first reactor

Ethylene to combustion products ... 0.3% 357 to 367 ° C and in the second reactor at 370 to

Ethylene to other products was 0.4% 380 ° C.

Under these conditions the total

The yield of 1,2-dichloroethane, 1,1,2-trichloro conversion of ethylene 99.7% and of chlorine _{water ethane and 1,1,2,2-tetrachloroethane was 95.0%, ao} material 91 ° / O.

based on the ethylene used. When the conversion of ethylene to 1,2-di-

rvt, j. Y ^ / η? » j. YK χ Y ^ - κ <; ■ in chloroethane, 1,1.2-trichloroethane and 1,1,2,2-tetra-

(Xb + Xc) / (Xa + Xb + Xcj - 15.5. Ϊ́υυ. Chloroethane is denoted by Xa, Xb and Xc

You can see that through the immediate introduction

part of the total air in the second reactor 35 Xa = 85.0: 100,

the relative yield of 1,1,2-trichloroethane and Xb = 7 0: 100

1,1,2,2-tetrachloroethane is increased noticeably. _ ''

Example 3

30 The conversion to the other reaction pro-

The procedure was as in Example 1, with the abutments distributed as follows:
Conversion that the catalyst support introduced into the first reactor with 5 percent by weight of ethylene to ethyl chloride 0.4%

Copper, 5 percent by weight potassium and 2 percent by weight ethylene to vinyl chloride 1.7%

Percent iron in the form of chlorides impregnates 35 ethylene to trichlorethylene 0.2%

and the temperature in the hot area of this ethylene to dichloroethylenes 1.4%

Reactor was 340 ° C. The results were the- as well as 0.4% products of combustion and

same as in example 1. other connections.

B is ρ ie 1 4 ⁴ ° ^ ' ^e total conversion of ethylene to 1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetra-

The operating conditions as in Example 1 were chloroethane was 95.5 ⁰ Ze.
modified to the effect that the catalyst carrier

of the second reactor with 5 weight percent copper, (Xb + Xc) / (Xa + Xb + Xc) = 11.0: 100.
5 percent by weight potassium and 2 percent by weight 45

Iron was impregnated in the form of chlorides and that became the temperature of the hot area of the

Temperature in the hot area of the second reactor increased during the second reactor to 388 to 398 ° C

360 to 370 ^° C. The results were that - all other conditions remained unchanged, so

same as in Example 1. The following results were obtained for the conversion

50 scored:

^eiSpie ethylene total 99.8%

A first reaction tube made of nickel with internal HCl a total of 93.2%

Diameter 32 mm was ethylene to 1,2-dichloroethane (Xa) 83.2% with a catalyst

loaded. The carrier consisted of alumina balls 55 ethylene to 1,1,2-trichloroethane (Xb) .. 9%

with a diameter of 2 to 5 mm, the middle speci- ethylene to 1,1,2,2-tetrachloroethane (Xc) 3%

fish surface 0.9 mVg and the pore size 0.2 ethylene to vinyl chloride 1.8%

up to 8 μτη; The balls were with a solution of ethylene to trichlorethylene 0.2%

CuQ ₂ -2 H ₂ O and KCl impregnated. The weight of ethylene to dichloroethylenes 1.9%

ratio of CWAl ₂ O ₃ was 5: 100, the weight of ethylene to combustion products ... 0.6%

ratio of KZAl ₂ O ₃ was 3: 100. Ethylene to various others

A second Rcak products connected to the first 0.1%

tion tube with an inner diameter of 65 mm

charged with a catalyst, the carrier of which was just 95.2% of 1.4mVg and a pore size of based on the ethylene.
0.1 to 5 μΐη was; the catalytically active component was the same as in the first reaction tube. (Xb + Xc) / (Xa 4- Xb + Xc) = 12.6: 100.

509 548/425

When working under pressure, the distance between the mean specific surface area of the catalyst supports in the first and second catalyst zones be smaller than when at atmospheric pressure adjacent pressure is being worked.

Example 6

The reactor system according to Example 5 was charged with a catalyst, the carrier of which was alumina spheres with a diameter of 4 to 7 mm, the mean specific surface 0.9 m ² / g and the pore size 0.2 to 8 μm, containing 5 percent by weight of copper and 3 percent by weight Potassium in the form of their chlorides were impregnated.

The catalyst support in the second reactor consisted of alumina spheres with a diameter of 4 to 7 mm, which had an average specific surface area of 1.4 m ² / g and a pore size of 0.1 to 5 μm and had been impregnated like the spheres in the first reactor.

The total feed rate of ethylene was 6 mol / h · 1 catalyst.

The molar ratio of HCl to C ₂ H ₄ was 2.30 and O ₂ to C ₂ H _{4 was} 0.65.

When entering the first reactor, the pressure of the reactants was 7.5 bar absolute and held at 6.8 bar on entry into the second reactor.

It became a hot range from 350 to 360 ° C in the first reactor and from 370 to 380 ° C in the second Reactor observed.

The conversion results were as follows:

Total ethylene (Xg) 99.2%

Total HCl (Yg) 93.5%

Ethylene to 1,2-dichloroethane (Xa) 83.4%

Ethylene to 1,1,2-trichloroethane (Xb) Ethylene to 1,1,2,2-tetrachloroethane

(Xc)

Ethylene to vinyl chloride

Ethylene to dichloroethylene

Ethylene to trichlorethylene

Ethylene to Combustion Products Ethylene to various others

Products

10%

4%

0.6 »/

0.6 «/

0.2 ° /

0.3 /

0.1 «/

lo The related to ethylene yield of 1,2-di chloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane was 97.4%.

It was found that the productivity is markedly improved by the application of pressure could.

The results obtained remained excellent; the!

is explained by the fact that the hottest

Extensive areas in the two reactors!

ao were than when working with a lower pressure

(Xb + Xc) / (Xa + Xb + Xc) = 14.4: 100.

^a 5 examples? and 8 (comparison)

Using the same reactors and the same catalyst beds as in Example 5, carried out two tests in which the

the ratio of the reactants HC1 / C., H ₄ and O ₂ / C ₂ H _{4 was} changed; the pressure on entry into the first reactor was 4.5 bar absolute and on entry into the second reactor 4 bar absolute.

A total of 3 moles of ethylene / h-1 catalyst

fed in. The hottest area in the first reactor was at 335 to 345 ° C and in the second reactor set at 349 to 359 ° C.

The results are summarized in the table below.

Example 7
1. reactor
entry

exit

2. Reactor outlet example 8
1. reactor
entry

exit

2. Reactor outlet

HC1 / C ₂ H ₄
O ₂ ZC ₂ H ₄

Xa + Xb + Xc
100 (Xb + Xc)
(Xa + Xb + Xc)

2.40
0.60

2.60
0.70

69.3 98.6 55 90.2 65.7 79.6 0.7 10.5 0 2.3 66.4 92.4

70.1 99.2 59 85 64.2 75 1.2 14th 0.4 4th 65.8 93

1.05

13.8 2.4

19.3

Xg: total conversion of ethylene,

Yg: total conversion of hydrogen chloride,

Xa: conversion of ethylene to 1,2-dichloroethane,

Xb: conversion of ethylene to 1,1,2-trichloroethane,

Xc: conversion of ethylene to 1,1,2,2-tetrachloroethane.

These two examples show that one reactor, i. H. with a catalyst zone, practical receives only 1,2-dichloroethane, while the invention Process allows, besides at the same time a considerable proportion of 1,1,2-trichloroethane and produce significant amounts of 1,1,2,2-tetrachloroethane, 11.4 and 15 percent by weight, respectively 1,1,2-trichloroethane and 2.4 or 4.3 percent by weight of 1,1,2,2-tetrachloroethane, based on the mixture of 1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane.

Example 9

A first reaction zone, consisting of a tube bundle with 30 steel tubes of inner diameter 30 mm and a length of 4 m, and a second reaction zone, consisting of another tube bundle with 13 steel pipes with an inner diameter of 50 mm, were connected in series.

Both reaction zones were charged with a catalyst which consisted of alumina spheres with a diameter of 4 to 7 mm, which had an average specific surface area of 0.6 m / g and pore sizes of 0.5 to 10 μm and with 5.9 percent by weight Cu ic form of CuCl ₂ -2 H ₂ O and 4.4 percent by weight of K in the form of KCl were impregnated. The total volume of the catalyst was 164 liters.

A gas mixture of ethylene, hydrogen chloride and air in total was put into the first tube bundle initiated corresponding to 3.3 mol / h 1 catalyst ethylene. The molar ratio of the reactants mer in feeding

O ₂ / C ₂ H ₄ = 0.75 and HClZC ₂ H ₄ = 2.19.

When entering the first tube bundle, the reactants were under a pressure of 4 bar, and when entering the second tube bundle, they were under a pressure of 3.3 bar.
The two tube bundle systems were each mi

xo provided a double coat in which a flowing capable heat exchanger circulated in such a way that the maximum temperature in the first tube bundle 355 to 365 ° C and the maximum temperature in the second tube bundle was 365 to 375 ° C.

The results for the conversion were as follows:

Total ethylene 97%

Total HCl 92%

Ethylene to 1,2-dichloroethane (Xa) .... 85% Ethylene to 1,1,2-trichloroethane (Xb) .. 8% Ethylene to 1,1,2,2-tetrachloroethane

(Xc)

Ethylene to dichloroethylenes

+ Vinyl chloride 1.5 °,

^a5 Ethylene to products of combustion

(CO + CO ₂ ) 1.5 «,

The yield of 1,2-dicliloroethane, 1,1,2-trichlo Ethane and 1,1,2,2-tetrachloroethane amounted to 94%, bi moved on the ethylene used.

(Xb + Xc) Z (Xa + Xc) = 9.6: 100.

Claims (1)

Claims: can be operated in a reactor with several reaction zones, which differ in the concentration of the catalyst, at temperatures of 232 to 371 ° C (US-PS 31 84 515). It is also known that oxychlorination can continue and lead to other chlorinated compounds of ethane and ethylene, e.g. B. to the dichloroethylenes, to trichlorethylene, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane. However, according to the 1. Process for continuous production
of 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane in addition to 1,2-dichloroethane by oxychlorination of ethylene, with a gas mixture from
Ethylene, hydrogen chloride and a gas containing molecular oxygen in two consecutive touching or separated ones
Zones of customary, known processes deposited on a carrier, in particular those in which oxychlorination catalysts in fixed beds which one and the same catalyst is reacted in a single form at elevated temperature, umpteen reaction zones, are not significantly characterized by the fact that the same amounts are used of saturated compounds with a) Prepare 2 carbon atoms in the first zone to a catalyst support, the higher chlorinated with an average specific surface area 15 as 1,2-dichloroethane, without simultaneously konvon smaller than 3 m ^ä / g and a pore width peting side reactions occur, such as the Verzwischen 0.05 and 10 μΐη, and in the second combustion and partial oxidation of ethylene and / catalyst zone a catalyst support with or the elimination of hydrogen chloride, which leads to an at least 10 «/ 0 larger but unsaturated chlorinated compound with 2 carbons 10 m ^s / g not exceeding average specific atoms of matter. Indeed the focus is of 1,2-dichloroethane in the hottest areas de; Catalyst zone, which is due to the exothermic Form the course of the reaction, little, and there is practically no formation of 1,1,2-tri