DE1518166B - Process for the production of vinyl chloride, vinylidene chloride and 1.1.1-trichloroethane - Google Patents

Description

The invention belongs to the group of processes for the chlorination of ethane, the thermal and not work catalytically. The invention also dispenses with inert diluents such as hydrogen chloride or steam, which burden the process and e.g. B. according to the German patent 955 057 are necessary.

It was initially assumed that higher temperatures would lead to the formation of unsaturated constituents, such as vinyl chloride (from dichloroethane) would have to favor and in particular would lead to the undesired formation of ethylene (from ethyl chloride) (cf. Ind. Tight. Chem. 41, 1940).

In other words, it became general ahgenomnien ;, that a decrease in temperature also leads to a decrease in the elimination of hydrogen chloride would have and therefore a corresponding reduction in the yield of both vinyl chloride and also of ethylene. A reduction or avoidance of the formation of ethylene would be very desirable been, with the disadvantage, however, that a reduction in the temperature in the procedure after the older processes lead at the same time to reduce the yield of desired ingredients, namely

1. of methyl chloroform, which is increasingly becoming a sought-after solvent in the Introduces practice,

2. vinyl chloride,

3. vinylidene chloride.

While avoiding this disadvantage, the claimed method succeeds in obtaining a relatively high proportion of the desired compounds, while the amount of ethylene produced is not worth mentioning. This substantial advance and the reduction of considerable disadvantages are achieved according to the invention by working in temperature ranges that the current state technically regarded as inexpediently low.

ίο The chlorination of ethane on non-catalytic Paths is carried out according to the invention also at a pressure which is above atmospheric, possibly considerably above atmospheric.

From the above-mentioned article there is no indication that any of those mentioned there Try to reference or relate to a mode of operation other than atmospheric pressure could.

The effect of overpressure is not only not discussed in this article, but in the article not even mentioned.

Furthermore, such prior art methods have generally Umsetztemperaturefl in the order of 450 ⁰ C or requires it. These processes have resulted in the formation of little or no methyl chloroform and the formation of significant amounts of tar and other polymeric products which cause clogging and fouling. equipment as well as loss of yield

have. So far it has generally been necessary for the production of substantial amounts of ¹ AEII Methylchloroförm to make this connection in a separate Chlorierungsgang using 1,1-dichloroethane as Häuptbeschickungsmäteriäl. However, this process is quite expensive to operate and is well known to have a tendency to deposit excessive amounts of carbon. If this tendency is suppressed by the use of diluents, the efficiency of the system suffers ^

A process for the production of vinyl chloride, vinylidene chloride and 1,1,1-trichloroethane by chlorinating ethane to form a mixture of chlorinated hydrogens has now been found, which is characterized in that one essentially consists of ethane, chlorine and a saturated chlorinated ethane A mixture consisting of 1 to 3 chlorine atoms in the molecule with a molar ratio of free chlorine to ethane, of about 1.5 to about 3: 1 at 345 to 440 ⁰ C uiid under an absolute pressure of about 1.7 to. 8 kg / cm ^{2 is} reacted in the absence of a catalyst, then the reaction mixture obtained is drawn off and separated and the 1,1-dichloroethane and the chloroethane are returned to the reaction zone.

An improvement is that at least a portion of 1,1-dichloroethane is returned to the reaction zone and a molar ratio of elects free chlorine to ethah, which is in the range of 1.8 to 2.5: 1.

It is also advantageous that the absolute pressure at which the reaction takes place is 3.8 to 6.6 kg / cm ² .

The procedure according to the invention is advantageously such that a non-catalytic chlorination of ethane

or a normally gaseous hydrocarbon fraction rich in ethane, among suitable ones Temperature and pressure conditions is carried out as well as the implementation by applying a

considerable amount of one or more of the reaction products, such as 1,1-dichloroethane modified and moderated as a diluent for the implementation The composition of this diluent will depend on the desired Product distribution changed; This is explained using the following exemplary embodiments.

The production of methyl chloroform is favored by the recycling of ethylene chloride and Ijl-dichloroethane: For this purpose, the reaction conditions can be controlled so that the molar amount of ljl-dichloroethane consumed by the reaction is equal to the moles of vinyl chloride formed further 1,1-dichloroethane can be converted by reaction with hydrochloric acid in the liquid phase using an iron chloride catalyst or in any other well known manner. So z. B. 1,1-dichloroethane can be prepared by introducing vinyl chloride and hydrochloric acid in virtually stoichiometric amounts into a liquid reservoir of 1,1-dichloroethane which is about 0.1 to 5 percent by weight, e.g. B. 0.5 weight percent iron (III) chloride (FeCl ₃ ) contains. The liquid is expediently passed through a heat exchanger in order to keep the temperature of the reservoir at 38 to 66 ° C. by dissipating the exothermic heat of the reaction. It has proven advantageous to carry out this reaction at an absolute pressure of 3 S to 4 ^! 5 kg / cm ² , thereby reducing the loss of the decomposition product in the small amount discharged which contains mostly unreacted hydrochloric acid; The reaction vessel is provided with a device for drawing off the formed dichloroethane as a liquid into a rapid distillation system or other suitable system which separates the reaction product from the dissolved catalyst:

In addition to the recycling of the dichloroethane it is advisable to carry out a complete return of the ethyl chloride. Thus, education can of vinyl chloride, ethyl chloride and ljl-dichloroethane can be practically avoided as an end product. In all the exemplary embodiments, they are used for charging coming products through the reaction chamber at such a speed resulted in the vaporized reaction mixture having an average residence time of about 15 seconds remains at the reaction temperature.

¹ S example 1

A feed mixture of 0.441 moles of ethane,

0.105 mol of ethyl chloride, 0.669 mol of 1,1-dichloroethane and 1 mol of free chlorine is injected into a continuously operating reaction vessel which is operated at an absolute pressure of 5.9 kg / cm ² and an average temperature of 417 ^° C. and a maximum temperature 427 ° C is maintained. Under these conditions it was found that 0.112 mol

Ethyl chloride were formed, resulting in a pure formation of ethyl chloride of 0.007 mol. It it was also found that 0.175 moles of 1,1-diehlorathan were consumed, while 0.175 moles of vinyl

cblorid were trained. The total amount of

30. The latter compound is then used for implementation : with hydrochloric acid in another reaction vessel to replace the used 1,1-di-

; Chloräthans implemented, whereby a whole

! seen formation of vinyl chloride equal to zero

results. The following Table I shows the complete

Composition of the emerging translation product.

Table I moles per mole of C 1-4 feed

Charging of the escaping
product

Really
educated

Educated
Oil percent

Vinyl chloride

Ethyl chloride

Vinylidene chloride

1,1-dichloroethane

1,1,1-trichloroethane

1,2-dichloroethane

1,1,2-trichloroethane

Different connections

0.105
0.669

0.175
0.112
0.062
0.494
0.189
0.010
0.012
0.007

0.007

0.062

0.189

0.010

0.012

0.007

2.4
21.6

65.9
3.5
4.2
2.4

These numerical values show that the method according to the invention can easily be used to produce a Product can be used that has more than 60 mol percent 1,1,1-trichloroethane, more than 20 mol percent Vinylidene chloride and less than 15 mole percent of the less useful reaction products. ; ;

Example 2

The production of vinylidene chloride can be significantly increased by including methyl chloroform (ljl, l-trichloroethane) be increased in the cycle. The methyl chloroform will dissolve under the action of heat with formation of vinylidene chloride and chlorine

decompose hydrogen. Thus, by the chlorination reactions developed exothermic heat tint according to the invention for the decomposition of methyl chloroform be used, whereby one achieves even higher yields of aD vinylidene chloride. Simultaneously 1,1-dicblorethane is recycled, whereby its subsequent chlorination gives a source of methyl chloroform. The following numerical values serve to explain the application of the to be attributed Methyl chloroform.

It is a mixture of 0.411 mol of ethane, 0.090 mol of ethyl chloride, 0.558 mol of 1,1-dichloroethane, 0.102 mol of methyl chloroform, 0.012 mol of various other compounds and 1 mol of free chlorine - as shown in Table II - introduced into the reaction vessel, which at an absolute pressure of 5.90 kg / cm ² and an average temperature of 391 ° C and a maximum temperature of 400 ° C. It is found that 0.159 moles of 1,1-dichloroethane are consumed and 0.183 moles of vinyl chloride are formed. Reacting 0.159 moles of vinyl chloride with hydrochloric acid in a separate reaction to replace the 1,1-dichloroethane consumed results in that which is actually formed

ίο Amount of vinyl chloride decreased by 0.159 moles.

In the following Table II, the results of the experiment are summarized, it being seen that in in this way a reaction product can be obtained which has more than 50 mol percent vinylidene chloride and contains 20 mole percent or more of methyl chloroform.

Table II. Moles per mole of Cl ₂ feed

Escaping Actually Educated cmcKung product educated Mole percent 0.003 0.183 0.021 7.3 ^; 0.090 0.098 0.008 2.8 ^; 0.170 0.170 59.0 0.006 0.010 0.004 1.4 0.558 0.399 0.000 0.0 0.102 0.160 0.058 20.1 0.002 0.014 0.012 4.2. 0.013 0.013 4.5 ^u 0.001 0.003, ^: 0.002 0.7 ⁱ

Vinyl chloride

Ethyl chloride

Vinylidene chloride,

1,2-dichloroethylene

1,1-dichloroethane,

1,1,1-trichloroethane

1,2-dichloroethane

1,1,2-triehlorethane

Different connections

Example 3

If the formation of vinylidene chloride is not particularly desired, the 'reaction conditions can be adjusted so that the formation is balanced by 1,1-dichloroethane without applying vinyl chloride. Thus, the total amount of vinyl chloride formed can be deducted as a finished product. Using the following Numerical values will explain this working system.

It becomes a mixture of 0.599 mol of ethane. 0.313 mol of ethyl chloride, 0.582 mol of 1,1-dichloroethane and 1 mol of free chlorine are pressed into the reaction vessel, which is at an absolute pressure of 5.9 kg / cm ² and an average temperature of 417 ° C with a maximum temperature of 427 ° C is held. The results obtained are shown in Table III below.

Table III Moles per mole of Cl _{2 feed}

Escaping Actually Educated NICKING product educated Mole percent 0.120 0.120 38.7 0.313 0.315 0.002 0.6 0.023 0.023 7.3 0.001 0.001 0.3 0.582 0.606 0.024 7.6 0.124 0.124 39.9 0.013 0.013 4.2 0.004 0.004 1.4 0.000 0.000 0.0

Vinyl chloride

Ethyl chloride

Vinylidene chloride

1,2-dichloroethylenes

1,1-dichloroethane .........

1,1,1-trichloroethane

■ 1,2-dichloroethane .........

1,1,2-trichloroethane ...
Different connections

Example 4

It was also found that the total amount of 1,2-dichloroethane and 1,1,2-trichloroethane formed as a result, there can be practically no need for these compounds to be fed back into the reaction can be achieved without causing any discernible adverse effects. The following Numerical values serve to explain this finding.

A mixture of 0.433 mol of ethane, 0.083 mol of ethyl chloride, 0.490 mol of 1,1-dichloroethane, 0.157 mol of methyl chloroform, 0.004 mol of 1,2-dichloroethane, 0.027 mol of 1,1,2-trichloroethane and 1 mol of free chlorine is poured into the reaction vessel pressed in, which is maintained at an absolute pressure of 5.48 kg / cm ² and an average temperature of 398 ° C at a maximum temperature of 412 ° C. These results obtained are shown in Table IV.

Table IV Moles per mole of Cl _{2 feed}

■ J * ηΛΜ4 Λίπΐη flP Escaping Actually Consumed Educated X) CSCnICKUBg product educated Mole percent Mole percent 0.008 0.167 0.159 37.6 0.083 0.098 0.015 3.5 0.124 0.124 29.3 0.012 0.012 2.8 0.490 0.382 22.0 0.157 0.260 0.103 24.4 0.004 0.011 0.007 1.7 0.027 0.023 114.8. 0.003 0.003 0.7

Vinyl chloride

Ethyl chloride

Vinylidene chloride

1,2-dichloroethylenes

1,1-dichloroethane

1,1,1-trichloroethane

1,2-dichloroethane

1,1,2-trichloroethane

Different connections

Example 5

This system can also be carried out using methyl chloroform or a mixture of methyl chloroform and ethyl chloride are operated as recycled products. The following numerical values serve to explain this system.

A mixture of 0.582 mol of ethane, 0.110 mol of ethyl chloride, 0.603 mol of methyl chloro: orm, 0.008 mol of ¹ 1,2-dichloroethane and 1 mol of free chlorine is injected into the reaction vessel, which at an absolute pressure of 5.9 kg / cm ² and an average temperature of 416 ° C with a maximum temperature of 427 ° C. Table V shows the results of this experiment. In this way it is possible to obtain 1,1-dichloroethane in high yield, preferably over the other reaction products.

Table V Moles per mole of Cl _{2 feed}

Escaping Actually Consumed Apprenticeship -mcKung product educated Mole percent Mole percent 0.089 0.089 22.1 0.118 0.150 0.032 8.0 0.117 0.117 29.1 0.002 0.002 0.5 0.156 0.156 38.8 0.603 0.555 8.0 0.008 0.011 0.003 0.7 0.003 0.003 0.7 0, COO 0.000 0.0

Vinyl chloride

Ethyl chloride

Vinylidene chloride

1,2-dichloroethylenes

1,1-dichloroethane

1,1,1-trichloroethane

1,2-dichloroethane

1,1,2-trichloroethane

Different connections

Examples

A Gemisct of 0.327 mol of ethane, 0.142 mol of ethyl chloride, 0.502 mol of methyl chloroform, 0.006 mol of 1,2-dichloroethane and 1 mol of free chlorine is pressed into the reaction vessel at an absolute pressure of 6.1 kg / cm ² and an average Temperature of 402 ° C is maintained with a maximum temperature of 412 ° C. Table VI shows the results obtained here.

On the basis of a comparison of the results according to Example 5 it can be seen that the higher chloroethane ratio or greater dilution of the ethane

charging with chlorinated ethanes according to Example 6 comes into use, to an enlarged training on vinylidene chloride preferably leads to the formation of 1,1-dichloroethane.

209 553/540

table VI
Möib pro MbI Cla-loading

10

feed

Escaping
product

Actually
educated

Consumed
Mole percent

Formed mole percent

Vinyl chloride.;.; .........

Ethyl chloride: ...: .......:.

Vinylidene chloride

1,2-dichloroethylenes

1,2-dichloroethane

1,1,1-trichloroethane

1,2-dichloroethane

1,1,2-trichloroethane

Different connections

0.142

0.502
0.006

0.149
0.007
0.334
0.017
0.032
.0,304
0.001
0.005
0.027

0.149

0.334
0.017
0.032

0.005
0.027

95.0

39.4 83.3

26.4

59.2 3.0

5.7

0.9

4.8

By adding l, i-dichloroethane to the recycled product, such conditions can be achieved, that an equilibrium with respect to the methyl chloroform is reached, so that there is an actual yield at this connection from practically nuÜ results. This is explained using the following example.

When the 1 7 mix is pressed into the reaction vessel, the

. . an absolute pressure of 5.95 kg / cm ² and one

It is 0.485 mol of ethane, 0.113 mol of ethyl chloride, 25 average temperature of 407 ° C at a

0.274 mol of l-dichloroethane, 0.405 mol of methylchloro-maximum temperature of 427 ° C is maintained. In

form, 0.002 mol of 1,2-dichloroethylene, 0.005 mol of 1,2-di- of Table VII are the results of this experiment

combined with chloroethane and 1 mole of free chlorine.

Table VII
Moles per mole of C ^ charge

feed

Escaping
product

Actually
educated

Consumes Mölp'rbzent

Äüsgeb'hdfet MÖlprözeni

Vinyl chloride

Ethyl chloride

Vinylidene chloride

1,2-dichloroethylenes

1,1-dichloroethane

1,1,1-trichloroethane

1,2-dichloroethane

1,1,2-trichloroethane

Different connections

0.113

0.002
0.274
0.405
0.005

0.126
0.128
0.135
0.005
0.290
0.396
0.012
0.007
0.002

0.126
0.015
0.135
0.003
0.016

0.007
0.007
0.002

2.2

40.5 4.8

43.4 1.0 5.1

2.3 2.3 0.6

The essential conditions for achieving the desired results are as follows: (1) a reaction temperature above 345 ° C. and preferably below 440 ° C., preferably from 370 to 427 ° C., (2) an absolute reaction pressure of about 1.7 to 8 kg / cm ² , preferably from 3.8 to 6.6 kg / cm ² , (3) an average residence time of the gases in the reaction zone of at least 5 seconds and preferably 10 to 15 seconds, (4) a molar ratio of free chlorine to that Ethane in the feed from about 1.5: ί to 3: 1 and preferably 1.8: 1 to 2.5: 1, (5) the application of a suitable amount of a diluent which contains a chlorinated alkane which is below the Above reaction conditions can experience an elimination of hydrogen chloride, whereby the Ümsetzungstemperaiur is regulated to the desired value, ie a chlorinated ethane containing 1 to 3 chlorine atoms per molecule. Thus, the charge typically has a molar ratio of 1,1-dichloroethane to free chlorine of from 0 to 0.7: 1 and preferably from 0.3: 1 to 0.65: 1 and has a molar content of ethyl chloride to free chlorine yon 0 to about 0.4: 1, preferably about 0.05: 1 to 0.4: 1, and in particular a ratio which results in recycling of the total amount of ethyl chloride exiting the reaction zone. If a high yield of vinylidene chloride is desired, the feed should also preferably have a mol ratio of 1,1,1-trichloroethane (methyl chloroform) to free chlorine of about 0.1: 1 to about 0.6: 1, and preferably 0 , 1: 1 to 0.2: 1.

The one that is used as a charge

Ethane is. preferably free of other hydrocarbons, but a C ₂ fraction with up to about 20% ethylene mixed with ethane can be used. . ,

The method according to the invention can be carried out without

Ϊ2

material formation and without explosions at the specified absolute pressures and ratios of chlorine to ethane can be carried out. Performing the procedure under pressure; leads to the advantage that the size of the translation system for a given capacity is considerably reduced, as is the reaction product at higher cooling temperatures can be obtained without recompression of the emerging from the reaction vessel Gases.

Another important advantage of the method is the possibility of distributing said mapping obtained by the _{chlorination:} products on a very small number of the total number of possible reaction products to restrict ini contrast saw this one sick .after the prior art always excessive difficulties a separation of pure industrially usable products from the involved product mixtures, which are normally obtained in the chlorination of hydrocarbons.

In the following, with reference to the F ig. 1 describes a typical embodiment of the non-catalytic process according to the invention for the chlorination of ethane. The drawing is a flow diagram showing suitable equipment. The flow diagram also shows the course of the implementation participants through the device. The products to be charged, namely ethane, chlorine and a recycled product stream containing ethyl chloride, l ^ l-dichloroethane and i, l, i-trichiorethane, are placed in the reaction vessel IÖ, which is located under an absolute pressure of 5.9 kg / cm ² is introduced through lines 1, 3 and 2, respectively. The reaction vessel is first heated to a temperature of about 427 ° C using a suitable arrangement, such as preheated ethane. After the temperature of the reaction vessel reaches a value of 345 ⁰ C, the reaction will be introduced with the desired speeds without preheating. The chamber 10 of the reaction vessel is made of a suitable alloy and is externally insulated against heat radiation. In general, the heat required is supplied by the conversion system itself.

There is no need for heat to be added or removed, with the exception of the amount of heat those introduced or withdrawn through the feed components and the emerging decomposition product will. The volume of the reaction vessel 10 is provided with respect to the intended charging rate that there is a residence time from about 5 to 30 seconds for the gaseous reaction mixture at the reaction temperature can.

The hot gases emerging from the reaction vessel 10 enter a tower 20 through a pipe 11. Here the small amount of heavy reaction products, such as tetrachloroethane and hexachloroethane, is removed via line 21, while the lighter reaction products are drawn off as top distillate and transferred to a separating drum 30 via lines 22 and 24 after cooling in a water cooler 23 to a temperature of about 38 ⁰ C. Part of the liquid condensate is fed back to the tower 20 via lines 31 and 32 as reflux. The excess condensate is fed to the tower 40 through the line 33.

The vapors are then transferred to the cooling unit 35 the line 34 is supplied. After cooling to a temperature of about -18 ° C with condensation out virtually all of the vinyl chloride present becomes the vapor-liquid mixture fed through line 36 to tower 40 for removal of the hydrochloric acid. the Gases emerging from the top of the tower 40 are passed through a cooled reflux head 41

ίο led, which is kept at a temperature of about -48 ° C and under an absolute pressure of about 5, (55 kg / cm ^, that is, it is a pressure that is slightly lower than the pressure in the reaction ^: The vessel is OK. The gas withdrawn as the top distiÜat,

which consists essentially of hydrochloric acid and ethylene, is eventually passed out of the system the line 42 withdrawn. The liquid condensate, which is a mixture of the desired chlorinated Containing hydrocarbons is called the soil fraction withdrawn from tower 40 via line 45, and a portion of this soil fraction is withdrawn through line 43 and the reheater 44 returned. The withdrawn liquid bottom fraction is sent to a distillation tower 50 to remove the vinyl chloride

factions fed ........

The tower top distillate, which contains essentially pure vinyl chloride, is passed through cooler 52 guided via line 51. Part of the condensed liquid is returned to the tower as reflux via the pipe

device 53 supplied again. The vinyl chloride product is withdrawn via line 54. Recirculation the bottom fractions by a heater 56 via line 55 is maintained so as to provide a corresponding To achieve evaporation. The remaining portion of the chlorinated organic product is made up withdrawn from the tower 50 via line 57 and fed to a fractionation tower 60 for the ethyl chloride. The vapor withdrawn from this tower in the form of a top distillate contains essentially pure ethyl chloride and is passed through the cooler 62 via the line 61. Part of the liquid condensate is fed to the Turin in the form of a reflux via line 63. The ethyl chloride product will withdrawn via line 64 and fed to a return tank 130, where the same in the entire mixture to be returned to the reaction vessel is mixed in. The orbiting becomes re of the bottom fraction of the tower 60 is maintained by a reheater 66 via the line 65 so to keep the bottom fractions at the boil. The remaining organic product is via line 67 withdrawn and fed to a fractionation tower 70 for the vinylidene chloride. Here it is in the form of a Steam withdrawn from the tower at the top of the distillate,

which contains essentially pure vinylidene chloride, passed through the cooler 72 via the line 71. A Part of the liquid condensate is fed back to the tower in the form of a reflux 73. The product is withdrawn via line 74 and one

Storage vessel supplied. The circulation of the soil fractions is maintained by a reheater 76 via line 75 so as to reduce the

to keep fraction simmering. .

The remaining product is withdrawn via line 77 and a fractionation tower 80 for the 1,1-dichloroethane fed. The one in the form of a top distillate withdrawn steam from this tower, which consists essentially of pure 1,1-dichioroethane

13 14

and small proportions of cis and trans-dichloroethylene material acid are passed through the cooling coil 107 , contains, is presented by the cooler 82 via the line 81 to thereby the amount of in the vapor phase. Part of the condensate is reduced to the 1,1-dichloroethane lying on the tower to an amount that can be neglected in the form of a reflux via line 83. The condensed product passed. The remaining product falls back into the conversion vessel via the S, while the ver line 84 is withdrawn and the return tank 130 is supplied with remaining vapor from the system via the line 104 , where it exits into the entire system. The pressure in the reaction vessel will generate the amount of product for the reaction mixture, in this case being brought to an absolute value of 3.8 to 4.5 kg / cm ² . The circulating of the soil fraction of the held. The 1,1-di tower 80 withdrawn through line 108 is reached by reheater 86 via the io chloroethane product is reached in a flash evaporator line 85 , and through this arrangement 110 is introduced, which with a heating device, keeps this bottom fraction at the boil. That is equipped with a steam jacket 111. The remaining chlorinated organic product is evaporated from the product while it is withdrawn through a lower end via line 87 and drawn to the tightly packed or trimmed column 112 fractionation tower 90 for the methyl chloroform. Leads remains in the evaporation vessel. The iron (III) chloride catalyst in the form of a top distillate from this, the vaporous product withdrawn from the UmTurm, which was introduced into the settlement vessel. The top distillate containing essentially pure methyl chloroform is stripped off in the form of vapor and is fed through condenser 92 via line 91. passed through the cooler 115 via the line 114

A portion of the liquid condensate is returned to the tower 20 and re-enters a receptacle 116 for the liquid in the form of a reflux via line 93. Part of the liquid is fed into the column as. The remaining liquid is returned as final reflux via line 117 . The product withdrawn via line 94. "If you want to return small amounts of hydrogen chloride, vinyl chloride and Qi to the reaction vessel, some or all of the ethyl chloride-containing 1,1-dichloroethane - this amount of methyl chloroform, small amounts can be added to the Reaction vessel, the product emerging from the tower is fed to the return through the action of hydrogen chloride on the Ethyführungstank 130 via line 95. The oils are formed, which is present in the hydrogen chloride circulations in the bottom fraction of the tower by charging for the reaction vessel 100 - the Reheater 96 via line 95 - is preferably returned for holding back in tower 40. The remaining bottom fraction is withdrawn via line 97 by drawing the hydrogen chloride via lines 118. If for this bottom and 119 for the purpose of cleaning, or one If there is no other use for fraction, the same can optionally be sent directly to the return Guide tank 130 may be expedient to feed this mixture to a further fraction via lines 118 and 120 .
tioning, so as to obtain a 1,2-dichloro-In contrast to the cases where one essentially ethane-l, l, 2-trichloroethane fraction. This reaction products, such as vinyl chloride, vinylidene product, can then be prepared for the renewed recycling of chloride or methyl chloroform, but the production of 1,1-dichloroethane must be transferred to the tank 130 in the reaction vessel. relatively low feed ratio to chlorine

Where the process under such conditions ethane, a ratio of about 0.5 to 1.2 and above

conditions is operated that a complete delay 40 preferably 0.7 to 0.9 moles of free chlorine per mole of ethane

If you need 1,1-dichloroethane, you can do this in the feed. Good temperature control

for feeding the chlorination stage can be made by suitable slight changes in the

Replacement amount of 1,1-dichloroethane can easily be maintained as a result of the amounts of chlorine added,

obtained that part of the hydrogen chloride contains in addition to ethane and chlorine the charge /

a part of the vinyl chloride is implemented. 45 kung in this case further ethyl chloride as a thinner ^

For this purpose, hydrogen chloride and solvents and preferably exclusively other vinyl chloride can be used in approximately equal molar amounts of chlorinated hydrocarbons. The required amount via the lines 101,103 and 102 to the conversion of ethylene chloride or at least a main part of the vessel 100 are fed, where the same is expediently introduced into the same by recycling liquid reservoir of 1,1-dichloroethane 50 of the total amount formed in the process, that is at least 0.1 weight percent, e.g. B. ethyl chloride supplied. In this way, 0.5 percent by weight of iron (III) chloride catalyst is obtained which contains about 0.8 to 2 mol and preferably about 1.2 to. The mixture of 1,1-dichloroethane catalyst 1.5 moles of ethyl chloride in the feed per mole tor is through the heat exchanger 106 via the free chlorine. If line 105 is passed in the manner shown here in order to thereby operate the heat of reaction 55, one can advantageously remove a reaction and obtain the reaction vessel with a settlement product which has a temperature of 75 to 85 mol percent of 38 to 66 ^° C. and below an absolute - or contains more 1,1-dichloroethane, namely to maintain a pressure of 3.8 to 4.5 kg / cm ² . Together with smaller amounts of a limited amount of circulation, the catalyst is also used in a number of other useful products. So z. B. thoroughly dispersed state in the reaction 60 held a 85 mole percent 1,1-dichloroethane containing test vessel. The reaction takes place quickly under duct, also typically about 4 mol percent, practically quantitative formation of 1,1-dichloro vinyl chloride, about 2 mol percent vinylidene chloride, ethane. After the 1,1-dichloroethane has formed, about 6 mole percent 1,1,1-trichloroethane and about the same from the reaction vessel via the line will contain 2 mole percent 1,2-dichloroethane.
108 deducted. The inert gases in hydrogen chloride, 65 In Table VIII below, experiments on such as ethane are summarized by the reaction vessel which, for example, leads to the production of. These inert compounds together with 1,1-dichloroethane by means of direct chlorination of a small proportion of unreacted hydrochloride-ethane according to the procedure according to the invention

reproduce. The conversion vessel used here, additional equipment and working methods for separating off the reaction products are practically the same as those described above have been.

The numerical values shown in Table VIII show that the process according to the invention can easily be operated with ethane conversions above 40 ° / ₀ , while at the same time a selectivity for 1,1-dichloroethane of about mol percent is achieved. Furthermore, the numerical

values that one can adjust the working conditions so that the process with respect to the ethyl chloride is practically in equilibrium, d. that is, the process can easily be operated under such conditions that neither the formation nor the consumption of ethyl chloride occurs when viewed from the outside, d. that is, the amount of ethyl chloride formed during the process is practical Equilibrium with the amount of ethyl chloride is,

ίο which is needed as a diluent for the charge will.

Table VIII Preparation of 1,1-dichloroethane

Attempt no. 10 8th 9 1.204 1,270 - 1.204 1,000 1,000 1,000 1.368 1,360 1.371 5.48 5.48 5.48 413 413 413 408 408 408 14.3 14.1 14.3 0.018 0.016 0.015 1.297 1.373 1.336 0.006 0.001 0.006 0.327 0.318 0.335 0.025 0.016 0.023 0.011 0.010 0.011 4.7 4.3 3.8 - 3.5 - 1.6 0.2 1.5 84.5 85.0 85.5 6.4 4.3 6.4 2.8 2.7 2.8 44.0 46.0 46.6 5.2 - 2.6

Charge, mole percent

Ethane

chlorine

Ethyl chloride ■

Implementation conditions

Absolute pressure, kg / cm ²

Maximum temperature, ⁰ C

Average temperature, ⁰ C

Dwell time, see

Reaction products, mol

Vinyl chloride

Ethyl chloride

Vinylidene chloride

1,1-dichloroethane

1,1,1-trichloroethane

1,2-dichloroethane

Actually formed, mole percent
Chlorinated products actually formed

Vinyl chloride

Ethyl chloride

Vinylidene chloride

1,1-dichloroethane

1,1,1-trichloroethane

1,2-dichloroethane

Actual consumption mole percent of the feed

Ethane

Ethyl chloride

1 sheet of drawings

209 553/540

Claims (3)

Patent claims: 1. A process for the preparation of vinyl chloride, vinylidene chloride, and!,!., I-trichloroethane by chlorinating ethane to form a mixture of chlorinated hydrocarbons, characterized in that one essentially consists of ethane, chlorine and a saturated chlorinated ethane with 1 to 3 Chlorine atoms in the molecule consisting mixture with a molar ratio of free chlorine to ethane of about 1.5 to about 3: 1 at 345 to 440 ° C and under an absolute pressure of about 1.7 to 8 kg / cm ² in the absence of a catalyst , then the reaction mixture obtained is drawn off and separated and the 1,1-dichloroethane and the chloroethane are returned to the reaction zone; 2. The method according to claim 1, characterized in that at least part of 1,1-dichloroethane returned to the reaction zone and a molar ratio of free chlorine to ethane selects, which is in the range of 1.8 to 2.5: 1. 3. The method according to claim 1, characterized in that the reaction is carried out at an absolute pressure of 3.8 to 6.6 kg / cm ² .