DE1618781B - Process for the partial chlorination of methyl chloride and or or methylene chloride - Google Patents

Description

Temperatures at which the heat capacity of the reaction mixture is 30 cal / g-mol ⁰ C or more is heated, whereupon one

2. allowed the exothermic chlorination reaction to proceed in a reactor under substantially adiabatic conditions such that the reaction temperature rises at least 20 ⁰ C above the preheat temperature, but not higher than 450 ⁰ C, and a portion is carried out of the adiabatic temperature rise in the temperature range in which the reaction mixture has a heat capacity of at least 30 cal / g-mol ⁰ C, whereupon

3. the methylene chloride having a higher chlorine content than the starting material and / or Separate chloroform.

The starting material consists mainly of methyl chloride, methylene chloride or a mixture of these both connections.

If methylene chloride is to be produced, it exists the starting material mainly consists of methyl chloride. The methylene chloride is removed as the product, and the circulated methyl chloride contains only a small amount of methyl chloride, which is not easily extracted separated from the crude product. When chloroform or a mixture of chloroform and methylene chloride to be prepared, one can use methyl chloride, methylene chloride or a mixture both connections go out. Since methyl chloride is the most readily available raw material, it is It is advisable to work in such a way that part of the methyl chloride is in chloroform from the start and part is converted into methylene chloride, the Mehtylenchlorid or part of the same for further Leads to chlorination in the cycle. As a reaction heat from the addition of each additional chlorine atom of 24 kcal per mole in. Freedom is set, the total heat development per pass reduce if a part of the methyl chloride is only chlorinated up to the methylene chloride and / or some of the chloroform is formed from methylene chloride. The starting material can also be in small quantities on other compounds such as chloroform, carbon tetrachloride, hydrogen chloride and / or inert ingredients. The concentration of water, oxygen, free radical inhibitors, possibly catalytically active metal salts and other foreign substances in the reaction mixture kept as low as possible to avoid the formation of corrosive or otherwise undesirable Prevent by-products.

In a preferred embodiment of the invention, the starting material consists of a mixture at least 30 percent by weight methyl chloride, at least 30 percent by weight methylene chloride and Contains no more than 10 percent by weight of chloroform. Such a starting material is particularly suitable for simultaneous production of methylene chloride and chloroform without excessive heat and without encountering difficulties in product recovery or in distillation.

In order to maintain the correct heat balance in the reaction system, it is essential that the molar ratio of chlorine to partially chlorinated methane (methyl chloride and / or methylene chloride) in the starting mixture is in the range of 1: 3 to 1:12, preferably in the range of 1: 4 up to 1: 7. When the chlorine concentration is higher than a molar ratio of 1: 3, such a strong heat development may occur that the final reaction temperature exceeds 450 ⁰ C and form large quantities of carbon tetrachloride or even decomposition to carbon formation or possibly enters explosion. If the chlorine concentration in the starting mixture is lower than it corresponds to a molar ratio of 1:12, the reaction either proceeds too slowly or too much heat has to be supplied from the outside. In view of the exothermicity of the reaction, molar ratios in the range from 1: 4 to 1: 7 are preferred, especially when a mixture of methyl chloride and methylene chloride is used as the starting material.

It is an important feature of the invention that the method is carried out in such a way that the high Heat capacity, which the mixtures have under the specified conditions, is exploited. This Conditions in turn depend on two important properties, namely the critical temperature and the critical pressure of the reaction mixture.

In the case of a pure chemical compound, the critical temperature is that temperature above which the compound does not change from the gaseous state to, no matter how high a pressure the liquid state can be converted, and the critical pressure is the pressure that is required to liquefy the gas at the critical temperature. If you heat up a pure liquid compound Temperatures and pressures below the critical values mean that a certain boiling point is reached. As more heat is applied, the joint undergoes an easily noticeable transition from liquid state to gas state, their volume increases several thousand times and theirs Density becomes very low. But if you keep the connection at a pressure above its critical pressure, completely different processes take place when heated. When the connection is at its critical temperature is reached and then further heat is supplied, there is no normal boiling with the formation of the usual Instead of the gas phase, but the compound goes into a dense gas phase that of the liquid Phase can no longer be clearly distinguished. If above the critical temperature then more Heat is supplied, the density of this dense gas phase gradually decreases to about 50% that of the initial liquid phase, then to 30% and then maybe even 10 or 5%; the However, density remains much higher than the densities of ordinary gases under atmospheric conditions exhibit. In order to bring about this transition from the liquid phase to the dense gas phase, is a considerable supply of heat is required. The amount of heat that is needed to maintain the temperature increasing the compound in this critical temperature range by 1 ° C is much greater than the one that is required to keep the temperature in other parts of the temperature scale around the same Increase amount. In other words, the connection has a high heat capacity when it is heated above the area in which the critical temperature is, and the pressure is above the critical pressure lies.

The critical temperatures and pressures of some compounds used in the process of the invention are of interest are the following:

connection Critical
temperature
⁰ C More critical
pressure
at Hydrogen chloride
Methyl chloride
chlorine 51
143
144
245
263
283 81.6
65.9
76.1
60.9
53.8 '
45.0 Methylene chloride
chloroform
Carbon tetrachloride

If one now goes from the pure connections to the Mixtures of several constituents used in the process according to the invention are above, so are the critical temperatures and pressures for pure compounds are not easily applicable. Instead of this is expediently used in a rough approximation of the so-called pseudo-critical temperatures and pseudocritical pressures of the mixtures. The pseudo-critical temperature is the temperature which is obtained by taking the mean value from the critical temperatures of the components into account of the molar ratio in which they are present in the mixture. The pseudocritical temperature an equimolecular mixture of methyl chloride and methylene chloride is then z. B. (143 + 245 ° C) 0.5 = 1? 4 ° C. In the same way one can also use the pseudo-critical pressure for a determine the given mixture. From a purely scientific point of view, the values are pseudo-critical no exact physical properties of the mixture concerned. The physical properties are rather determined by the critical condensation temperature (»Cricondentherm«) and the maximum The pressure point of the liquid-vapor envelope ("Cricondenbar") is determined as it was by B. F. Dodge in "Chemical Engineering Thermodynamics", McGraw-Hill Publishing Co., New York, 1944, p. 545, is described. In the latter sizes, for. B. the relatively small volume of a real one Vapor phase taken into account that is still above the pseudo-critical pressure and at higher pressures can be present until the >> Cricondenbar «value is reached. Within the scope of the invention are but the pseudo-critical values are accurate enough for all practical purposes and relate to these values the critical temperatures and critical temperatures given below for the various mixtures Press.

When carrying out the process according to the invention, nuts maintain a pressure of at least 65 at which corresponds approximately to the critical pressure of a typical reaction mixture.

At pressures just a little above 65 atm, a small amount of a normal gas phase can still be present being. Although the concentration of chlorine in this phase can be slightly higher than in the rest of the Systems, this amount of chlorine is not so great that there would be a danger. Preferably the pressure is in the range from about 85 to 130 at, since no ordinary gas phase exists under these conditions. If necessary, pressures of up to about 150 atmospheres or even more can be used; special benefits will be but no longer achieved as a result.

The critical temperature depends on the components of the reaction mixture. If the reaction mixtures are rich in methyl chloride, the critical temperature is close to that of pure methyl chloride and chlorine, ie in the range from about 140 to 160 ^° C. If the starting mixtures are rich in methylene chloride, the critical temperature can vary depending on the amount of chlorine used in the general range of about 200 to 240 are C ^0. If the output material is substantial, e.g. B. contains about 30 weight percent each, of methyl chloride and methylene chloride, the critical temperature is between the ranges given above, that is between about 160 and 200 ^° C.

The typical starting mixtures used in the process of the invention have heat capacities of about 10 to 15 cal / g-mole ^° C. That is, 10 to 15 cal is required at temperatures outside the critical temperature range are to heat 1 g-mole of the mixture by I ^{0 C.} In the area of the critical temperature, on the other hand, the reaction mixtures have much higher heat capacities, e.g. B. those from 30 to 60 or 70 cal / g-mol ⁰ C or even more. The heat capacity of the various mixtures can be calculated according to the method described by Hougen, Watson and Ragatz in "Chemical Process Principles", 2nd edition, Verlag John Wiley & Sons, New York, 1960, part II, especially on p. 593, 611 and 617.

These high heat capacities of over 30 cal / g-mol ⁰ C have the various reaction mixtures at temperatures which are about 10 to 50 ⁰ C away from the critical temperature. In the case of some reaction mixtures, the heat capacity is indeed very high, but only over a relatively narrow temperature range. In other cases the heat capacity is only moderate, but over a wider temperature range. The highest heat capacity of a given reaction mixture is usually slightly above its critical temperature.

Preheating is necessary to complete the chlorination reaction within an economically viable time trigger. The “preheating temperature” here is the temperature of the starting mixture has at that point of the reaction vessel behind which no further heat from him is fed from the outside. This point is usually the point at which the initial mixture from the preheater exit. Under certain circumstances, the starting mixture can remain in the preheating zone a little longer. in which case the exothermic heat of reaction has already brought it to a temperature above the Temperature of the high pressure steam or other heat exchange medium in the jacket of the heater warmed up. In these cases, the preheating temperature becomes the highest temperature of the heat exchange medium understand in the jacket of the heater. If all the warmth is the starting material Chlorinated hydrocarbons used and / or the chlorine is added before they are mixed the preheating temperature is the temperature of the starting mixture immediately after mixing.

Working with preheat temperatures from 120 to 230 ⁰ C. At preheat temperatures below about 120 ⁰ C, the reaction jumps so slowly that it becomes uneconomical. In preheating; s above about 230 ⁰ C is the temperature range at which the reaction mixture unusually high

7 8

Has heat capacities, already largely over the range from 150 to 250 ⁰ C are the relative

stepped, and there is no longer the opportunity to chlorination _{rates CH 3} Cl: CH ₂ Cl ₂ : CHC1 ₃ the high heat capacity of the reaction mixture about 1.0: 0.7: 0.3. But if the temperature rises to 400

to take advantage of the fact that a temperature rise increases to up to 500 ^° C., the relative values approach

excessively high maximum temperature is prevented. 5 chlorination rates with a ratio of 1: 1: 1. For this reason, the preheating temperature may, if as little carbon tetrachloride as possible

lie only in the temperature range in which it should be, it is important that as large a part as possible

Reaction mixture has a heat capacity of minor chlorination reaction at the lower temperatures

at least 30 cal / g-mol ° C. ratures runs. With a typical preferred

Preferably, the preheating temperature must be within io embodiment of the invention is 50% of the GE-the range of about 180 to 230 ⁰ C., due to the effect of the howenn contains particularly entire chlorine consumption, the output product appreciable amounts of metal hen heat capacity at a temperature rise to thylenchlorid because at this higher only about 50 ⁰ C instead, and the remaining 50% of the chlorine preheating temperatures nor the high heat consumption cause a temperature increase of the capacity of the system and at the same time 15 maybe 150 ⁰ C, so that you get a good chlorine advantage higher reaction rates and need and a quick overall reaction is obtained. Can thus achieve shorter overall reaction times. These conditions are implemented as of

After preheating, the reaction takes place predominantly at temperatures that favor the formation

practically carried out adiabatic conditions. of the desired, partially chlorinated methanes

This means that no means are used to reduce the cost of carbon tetrachloride formation.

to supply heat to the reactants or cheap.

to withdraw. The reaction vessel is preferably The reaction can be batchwise or continuously

isolated so that the heat of reaction is retained borrowed in various types of reaction vessels, e.g. B.

and the implementation in a short time, e.g. B. about 1 Mi- in stirred autoclaves, tubular reactors and pipelines

ute, runs completely. Through the isolation, 25 processing reactors will be carried out. Solid packing

an unnecessary dissipation of the heat in the and / or catalysts are not necessary,

surrounding work area. but can be used if desired.

The temperature rise in the adiabatic range, the reaction is preferably continuous in

The reaction conditions must be at least 20 ° C; a packed-body-free pipeline reactor

however, the highest reaction temperature must not exceed 30, the length of which is at least 125 times its length

450 ⁰ C lie. When the temperature rise is not within the inner circumference. In such a reactor

is at least 20 ⁰ C, the chlorination achieved is a laminar flow at Reynolds> numbers

degree too low. Preferably the temperature should take place above 5000, and as a result only a very high one occurs

rise be at least 100 ⁰ C and the highest low backmixing. The free chlorine is

Reaction temperature in the range of about 300 to 35 going through reaction with the methyl chloride and

450 ⁰ C lie. When the maximum temperature is 450 ° C or consumes methylene chloride. As soon as the

, large amounts of carbon tetrachloride are formed - chloroform concentration becomes relatively high,

substance, since the higher temperatures are the formation of the free chlorine is already largely used up

favor more chlorinated derivatives. Furthermore, has been. Therefore, at no point in the reaction

at temperatures significantly above 450 ⁰ C the risk of a combination of conditions under

strong coking and / or explo-

siorieri is mutilatingly increased, carbon-favored, and in the same

The main quantities, of which the early occurrence of a relatively high chlorine

reached maximum temperature depends on the concentration of form, a relatively high chlorine

45 concentration and a relatively high Τοπία) the composition of the starting quality exists. ...

used chlorinated hydrocarbons, the reaction vessel can be generated from any bcheb

. .... · .. consist of the material, the reaction pressure, and the

b) Resists the molar ratio of chlorine to the chlorinated carbon chemicals. Preferred ¹ Werkwasserstpffen and ... ■ 50 substances for the high temperature part of the device are

■■ ',,. ., nickel-rich alloys that still contain chromium or

c) the preheating temperature. contain lybdenum. These can either be on their own

,. . alone or as linings on: other metals If the starting material has already been used in significant quantities. For the low temperature parts of the Contains chlorofprm, so this, especially with the 55 device can be different, mild steel or lower temperatures, not easily chlorinated. If stainless steels are used, a substantial amount of carbon tetrachloride is generally present as starting material is, this is not chlorinated at all chlorinated hydrocarbons and the chlorine sepa- and therefore does not contribute to the generation of heat during the derl caused by two high pressure pumps on the gewiin reaction at. When the chlorine content of the reaction is brought to pressure, it can be cold or in the case of a mixture of rooms rises, the exothermic reaction temperature rises as well. This mixture warmth. The higher the pre-heating temperature is then passed through a heat exchanger, / .. I). the less heat capacity remains to be absorbed by a preheater, which is higher through its jacket The heat of reaction is available, and the higher the water vapor that flows. But you can also do that hence the final temperature. 65 chlorinated hydrocarbons used as starting materials. The relative rates of chlorination of the three, the chlorine or both before mixing partially chlorinated chloromethanes vary greatly in erhil / eu, in which case after. dem i'rliit / en only Dependence on the temperature. Little or no additional heat can be supplied at high temperatures

9 10

needs. If the substances are circulated, G) The process is very varied by adding it

this can be done at elevated temperatures and / or the production of methylene chloride and chloro

increased pressures. form in almost any ratio in the

The total reaction time from the point in time allowed to the same system,

which the reactants from the preheater are exposed to. 5 _{H) The reaction takes place quickly> often in less than}

^tT A ^te u \ · l ^TO i? α ^P "b ^Z] l _P ™ ^{n te from a min">} and can be still in a

adiabatischerr part of Reaktjorisgefaßes leak, _{simply built Occasion practical} ti _S ch under con-

Usually takes about 0.5 to 3 minutes, usually trolls hold

about 1 to 1.5 minutes. At the end of this period

if the chlorine is usually completely consumed, ίο I) Since the reaction products are already under high

but when the pressure is at the highest reaction temperature, it is very easy to find at least one

Range from about 250 to 450 ⁰ C. ' Part of the subsequent distillation at increased

The product or products can be carried out at known pressure, and this in turn can be obtained; This is usually followed by distillation, which facilitates the separation of the hydrogen chloride. If the reaction is carried out continuously from the methyl to be recycled, the desired product chloride will be significant,
or the desired products and the undesired ones

Products (mainly hydrogen chloride and tetra- In the following examples a pump for the

chlorocarbon) continuously by distillation ent- chlorine and another pump for the mixture from the

removes, preferably up to a technically convenient 20 remaining components, namely methyl chloride (CH ₃ Cl),

feasible minimum content, while the rest in methylene chloride (CH ₂ Cl ₂ ), chloroform (CHCl ₃ ), Te-

Cycle is performed. carbon trachloride (CCl ₄ ) and hydrogen chloride (HCl),

The inventive method offers numerous uses. The starting materials come under the

Advantages: pressures given in the examples of these

25 pumps, d. H. at pressures above the critical

A) By working above the critical pressures of the mixtures, which are around 65 at. This Pressure and the resulting avoidance of substances are mixed under the high pressure and a substantial amount of normal steam fed to a preheater consisting of a 9.525 mm phase, one avoids the difficulty of a 16.76 m long nickel tube. the lent high chlorine concentration in the steam preheater is surrounded by a jacket in which phase, d. H. a concentration of chlorine, a lot of high-tension water vapor or some other high temperature is as the one in the liquid phase, and can be a medium of exchange. After flowing through easily lead to the formation of explosive mixtures. starting mixture on the table below

B) indicated by the use of high preheat temperature Wärmekapazi- ³⁵ The vorertät of the reaction mixture to avoid m reaches the mixture mtzte a pipeline reactor need for a large amount ^of an inert ~ fg ^luhtem. ^ ^ CTEL hrom-Sto ^{hlrol! r. of} reaction medium (such as carbon tetrachloride) J ^{mm in} diameter and 30.48 m in length, which is surrounded by one and the resulting need for a I ^{0 C} J "thick tube, solatu> n. In this separation and circulation of such a ⁴ ° In the reaction vessel, the reaction medium given in the examples, the highest reaction temperatures are reached.

At the end of the pipeline reactor, the reac-

C) By avoiding the inert reaction tion mixture by a pressure relief valve, the medium is at the same time the available Concen- after which the methylene chloride and or or the particular Chlorotration for the chlorination off form ₄₅ separated by distillation. The raw materials are increased significantly, and if more hydrogen chloride is also separated off and the methyl chloride is supplied to the reaction available for use in other processes. Also, the chlorine will primarily react with the excess amounts of carbon tetrachloride or methyl chloride, resulting in a significant separation. The methyl chloride and any higher reaction rate will result. ₅₀ amounts of methylene chloride, chloroform and tetra-

D) Because most of the conversion takes place in the case of chlorocarbons that have not been separated off, relatively low temperatures are carried out in a cycle.

out and the occurrence of temperatures above ^the examples are avoided in the form of the following 450 ° C, the yield is summarized in the table. In Example 1, the pre-desired products, namely methylene chloride 55 heating temperature and the chlorine concentration and / or chloroform, are increased and the output is relatively low, so that in this experiment a little more methylene chloride than chloroform is produced in the unwanted carbon tetrachloride. Example 2 I ^m are the chlorine concentration and the subsequent. . . ■ initial concentration of "methylene chloride something

E) The utilization of the chlorine is very good; they undergo _{6o higher> and hMet a little more} chloroform. Im carries practically 100 /, if the maximum Reac- _{Bej id} 3 _{is the initial} methyl chloride concentration

4 ° _n ⁿ o p ^S ™ ^{mperature range of about 25} ° ^BLS tion high and the chlorine concentration is low, so that

450 C. predominantly a conversion to methylene chloride

F) There is no need for an extremely effective heat output. In example 4, both are the initial exchanger to allow the methylene chloride concentration to run through the reactions as well as the preheating prevent this in processes other than tongue temperature and the highest reaction temperature Result of the high heat of reaction and / or high, with the result that predominantly a conversion high local chlorine concentrations occurs. treatment to chloroform takes place. In example 5 they are

Temperatures and the chlorine concentration are relatively high, and consequently high degrees of conversion are achieved and the chloroform concentration in the product is relatively high. In example 6, the chlorine concentration and temperatures are 12

relatively high, so that high degrees of conversion of methyl chloride to chloroform are achieved will. In all examples, the amount of carbon tetrachloride formed is only about 2 to 3% of the amount of chloroform formed.

Composition of the starting material,
Weight percent

CH ₃ Cl

CH ₂ Cl ₂

CHCl ₃

CCl ₄

HCl

Cl ₂

Composition of the product, percent by weight

CH ₃ Cl

OH2C-I2

CHCl ₃

CCl ₄ .... ·.

HCl

Ci ₂ :

Preheating temperature ⁰ C

Heat capacity at the preheat temperature

cal / g-mole ⁰ C

Pseudocritical temperature, ⁰ C

Highest reaction temperature ^{, 0 C}

Reaction pressure *), ata

Molar ratio (partially chlorinated methane) :( chlorine) .. Generation ratio kg CHCI ₃ / kg

CH ₂ Cl ₂

Generation ratio kg CClJkg

CHCl ₃

*) The pressure in the preheating stage is practically that

² example 3 4th ⁵ I. ¹ 38.15 48.78 35.70 31.22 44.19 47.48 32.64 49.96 43.72 41.38 0.12 7.51 2.70 5.57 0.22 0.24 0.46 0.06 0.34 0.49 0 2.27 0.63 0.12 0 14.01 8.34 10.95 19.03 13.72 33.92 42.39 31.69 24.87 40.76 52.89 40.86 52.12 48.36 47.29 5.52 9.67 9.72 16.30 4.23 0.40 0.50 0.24 0.57 0.61 7.19 6.52 6.23 9.90 7.04 0.08 0.05 0 0 0.07 150 163 221 205 148 30th 33 41 53 30th 181 169 184 183 175 198 191 343 372 195 96 98 96 89 96 6.7 12.0 8.6 4.4 7.1 1.0 0.3 3.3 2.3 0.7 0.03 0.02 0.03 0.02 0.03

34.13

41.21

19.29

21.90 51.40 15.99

0.65 10.06

0
211

43
180
400

89

same as the reaction pressure.

Claims (7)

1 2 and 350 ° C is implemented. Under these conditions, claims: should the reaction proceed "either in the liquid phase or in a highly compressed vapor phase". 1. Process for the partial chlorination of methyl- For chlorination of a volatile starting material, such as chloride and / or methylene chloride, da- 5 methane, this should, according to the information in the patent, be characterized in that ^before the chlorination in a solvent such as tetra, . ". ,, ,,, ™ _,,. ,. , ",,, chlorocarbon, can be dissolved. In the only exit • λ!? £ 7μ T ¹ Ji ^OlCh i ^r u ^d _t f ^1Sl ?, ^MO J management example that the production of a chlorine Describes methyl chloride and / or methylene ond _{methane compound} , methane is dissolved in tetra-pressure of at least 65 atm to 120 _{10 of chlorocarbon and then 3 to 4 mol} up to 230 C, but in this range only to _{CMor jj} mol methane at 240 bjs 25Q} o _{c md JQ at} such temperatures at which the Warme- _{h tsächlich m} carbon tetrachloride implemented. the capacity of the reaction mixture 30 cal reaction is carried out in a tube / the in g-mol C or more, heated, whereupon the _{liquid heat exchange} medium is immersed, which ^one , ^ ₁ , -, · 15 serves to set the reaction temperature essentially 2. to keep the exothermic chlorination reaction constant Reactors under essentially adiabatic chlorination reactions of this type are so powerful Conditions such that the _{exoth can easily decompose or even decompose} The reaction temperature is at least 20 C above the explosion. The carbon tetrachloride and the ^"5 S ^ ^{initially stem} P ^he _be J * ^tur '* calc not high _{2o fK} £ _{si heat exchange means in which Ve} r- than 450 C rises, and that part of the adiabatic _{def nth USA} patent is undoubtedly considered table temperature rise in the temperature _{Mittd used to} control the reaction ture area takes place in which the implementation is _{to be hooked due to this high concentration of Tetra} . mixed heat capacity of at least _{chlorocarbon but the effective} concentration 30 cal / g-mol C aufweht, whereupon _{üon the} compound _{to be chlorinated} and thus the 3. that reduces a higher chlorine content than the system's _{output capacity} . Fergangsgut containing methylene chloride and _{nef ü def nth US} A patent does not separate or vehicle or chloroform. special task, as high as possible 2. The method according to claim 1, characterized in the yield of methylene chloride and / or chloro draws, that a mixture is used as the starting material and the lowest possible yield of Tetra is used is to achieve the at least 30 weight percent chlorocarbon. Methyl chloride, at least 30 percent by weight. The partial chlorination of Methylene chloride and not more than 10 weight methyl chloride and / or methylene chloride in percent contains chloroform. done in a safe and extremely effective manner 3. The method according to claim 1 or 2, can be 35, if you have certain crucial characterized in that it keeps variables under control at a molar ratio such that the high Chlorine to methyl chloride and / or methylene heat capacity is used, the reaction chloride carried out in the range from 1: 4 to 1: 7 mixture under certain combination conditions will. of pressure and temperature. At this point 4. The method according to claim 1 to 3, characterized in that the reaction mixture includes 40 conditions characterized in that the chlorination stage at about a pressure exceeding its critical pressure 85 to 130 at is carried out. and at a temperature in a certain range 5. The method according to claim 1 to 4, characterized in relation to its critical temperature, as characterized in that the reaction mixture is described below. Due to the high heat, a temperature in the range of about 180 to 45 capacity which is pre-heated the reaction mixture under these be-230 ⁰ C. has special conditions, the implementation 6. The method according to claim 1 to 5, characterized in such a way adiabatically that a large one characterized in that the chlorination is absorbed under reaching part of the exothermic heat of reaction in the Reakchung a maximum reaction temperature in the tion mixture. Here the reac range goes from about 300 to 450 ⁰ C is carried out. 50 tion for the most part at relatively lower rates 7. The method according to claim 1 to 6, characterized in that temperatures in front of them which indicate the formation of methylene that at least one of the in the um- chloride and / or chloroform favor, and Settlement mixture contained, partially chlorinated, the reaction mixture never reaches the high Methane is returned to the starting material in the cycle - temperatures that lead to the formation of carbon tetrachloride will. 55 favor the substance, or even higher temperatures that lead to decomposition or explosion. At the same time you can control the temperature in Let rise way to such a high final value that the overall conversion is rapid and the chlorine 60 is practically completely consumed. In the USA patent 2 105 733 are various The inventive method for Teilchlorie- known method for chlorinating saturated tion of methyl chloride and / or methylene hydrocarbons and their partially chlorinated chloride is characterized in that one
Derivatives described. The patent specification itself concerns primarily processes in which elemental chlorine 65 1. a mixture of 1 mol of chlorine and 3 to 12 mol with the hydrocarbons or their derivatives methyl chloride and / or methylene chloride while maintaining a pressure between about 10 at a pressure of at least 65 at to 120 bis and 150 at and a temperature between about 100 230 ⁰ C, but in this range only to such