DE1468802A1 - New chlorination process - Google Patents

Description

Dr. Walter Beil , _n . .,. _OßK

Alfred Körner 2Ο.ΑρπΙ19β5

DrJIr ^ J-Ji ^ Wolff

Dr- I'iL-zr. ■■; ::;. Boil

Frankfurt a. bl- maximum j I '^

Adeionstrasse 58 - Tel. 312649 j - * -

Our No. 11.4-33

Pittsburgh Plate Glass Company Pittsburgh, Pen., V.Ot.A.

New chlorination process

The present invention relates to the production of chlorinated hydrocarbons. In particular concerns The present invention describes improvements in the production of chlorinated hydrocarbons by oxychlorination processes.

It is known in the art to use chlorinated carbons from aliphatic hydrocarbons and their incompletely chlorinated derivatives according to modified ones Deacon-type chlorination processes described in Technique known as the oxychlorination process. One oxychlorination process of the present type is the chlorination of hydrocarbons and / or chlorinated hydrocarbons with hydrogen chloride

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and an oxygen-containing gas such as air or elemental Oxygen in the presence of a metal halide catalyst and at elevated temperatures. In a process of this type it is assumed that the chlorine is hydrogen is added to elemental chlorine and / or water in the presence of the catalyst and in the same way Chlorine released from the hydrogen chloride reacts with the hydrocarbon or chlorinated hydrocarbon, the is contained in the supplied gas, converted to form further chlorinated hydrocarbons and HCl. The hot HCl obtained from this chlorination is then further processed, by converting it to chlorine in a Deacon reaction.

In another variation of the present oxychlorination processes elemental chlorine is used as a supply source. In this latter process, hydrogen chloride is used by chlorination of the supplied hydrocarbon and / or hydrocarbon chloride with elemental Obtain chlorine in the catalytic reaction zone. Free chlorine and an oxygen-containing gas, such as air or oxygen itself and a hydrocarbon and / or chlorinated hydrocarbon in contact with a Metallhalo ^ enidkatalysator brought on increased Temperature is maintained. The chlorine will likely settle with the hydrocarbon and / or chlorinated hydrocarbon with the formation of hydrogen chloride and a chlorinated derivative of the added organic substance around. The chlorine contained in the hydrogen chloride produced in this way is then used for further chlorinations used according to the conventional Deacon process, in which the hydrogen chloride is oxidized to water and elemental chlorine.

A number of problems arise with processes of this type because of the corrosive nature of the gases, which are explosive Conditions resulting from the presence of oxygen at elevated temperatures in the presence of organic Substances that can lead to instantaneous oxidation,

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may be present, and for other similar considerations. Proper mixing of gases and feeding the gases in the reaction zones is extremely important in oxychlorination processes, if these problems are to be minimized or avoided. Also makes the implementation these reactions in fluidized bed reactors occur because of the high speed of the fluidized particle layer flowing gases necessary that the gases mixed intimately and as quickly as possible to the appropriate Reaction temperature can be brought so that a complete conversion can take place before the gas mixture flows out of the layer. To have an exact dwell time of the converting materials in the fluidized beds and initiating the conversion so quickly as possible in the same, so that a full implementation can take place before the When gases leave the layer, care must be taken when supplying the gases. This is special important, because it is not always possible to use these layers due to the physical limitations of the system expand in the vertical direction to a height sufficient to achieve the exact dwell time.

According to the present invention, there has been provided a method for supplying hydrocarbons and / or chlorinated hydrocarbons, the chlorination agent and the oxygen to an oxychlorination reaction Developed in such a way that a precise implementation in the vortex light reactor under maximum Exploitation can take place. The invention ensures intimate mixing of the substances and reduces the risk of explosion and leads the gases within the reaction zones to a contact point where the temperatures sufficient to initiate the implementation immediately and also leads to a sufficient residence time within ; ': there is a reactor to complete the reaction before then ijcis ^ emiscii escapes from the layer.

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According to the present invention, a method for supplying oxygen to a fluidized bed is provided from catalyst particles for an oxychlorination process in which the oxygen is preheated by the catalyst particles that are in the layer before their contact with a mixture of chlorinated hydrocarbons and chlorinating agents are contained within the fluidized bed of catalyst particles. According to of the present invention is an oxygen supply system provided in such a way that the oxygen in the fluidized bed of catalyst particles in a sufficient Distance above the point of introduction of the hydrocarbon and / or chlorinated hydrocarbons and of the chlorinating agent is introduced. The oxygen is introduced so that it crosses the zone in which the chlorinating agent and the hydrocarbon and / or chlorinated hydrocarbon prior to contact with these or other feed materials are introduced so that the oxygen through heat exchange between the Catalyst particles and gases in the layer and the Oxygen supply lines to the reaction temperature or is brought near them. In this process, the oxychlorination reaction takes place immediately after initiation The oxygen takes place in the layer of catalyst particles as the chlorinating agent and. the hydrocarbon and / or chlorinated hydrocarbons have the reaction temperature at this point in the layer and the oxygen through a heat exchange between the catalytic converter part surfaces and gases in the bed and in the oxygen lines when traversing part of the fluidized bed brought the catalyst particles to this temperature became.

Purely a more complete understanding of the lying invention is based on Pig. I referenced showing a vertical section of a made up of many tubes Fluidized bed reactor shows.

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Pig. FIG. 2 is a vertical section of the lower part and part of the tubes 3 of FIG. 1.

Pig. 3 is a cross section of the pig. 2 along lines C-C.

Pig. Figure 4 is a cross-section along lines A-A the pig. 2.

The present invention relates Oxychlorierungsumsetzungen in which the reaction takes place in a fluidized bed of catalyst particles * In the description of fluidized beds in the application and in the claims, the term "fluidized bed ¹¹ is used in its broader sense. In the practice of the fluidized bed process, gaseous reactants with If a gas is passed through a layer of solid particulate material, several different conditions can occur depending on the gas velocities used, the size and density of the particles used and other similar considerations If the gas velocity is low, the layer of solid particles will remain static, but as the gas velocity in the layer is increased, some of the particles will become dynamic in the upward flowing gas flock suspended. As a result, the layer height is increased and a layer called a "dynamic layer" is formed. If the gas velocity is increased even further, all particles are suspended and the layer is expanded even more. Eventually the bed can assume an extremely turbulent state, which in many respects resembles a boiling liquid. The present method can be applied either in a dynamic layer or in layers corresponding to a boiling liquid. Both layers

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fall under the term "fluidized bed ¹¹ , as. for" is to be understood here. The exact.] 3e, conditions required to create one of these bed states of the type described above, depend on various factors, "^ .β, .β, .Β. particle size of the component layers, the _v grass speeds, the density of the catalyst particles and other similar considerations "Wilhelm &Kwauk" Ohemical Process Engineering, "Vol. 44 ·, p 201 (1948) describes the different Factors necessary to fluidize a bed and by following the rules discussed therein, the desired bed conditions can be created for any given group of gases or catalyst particles used.

In the process according to the invention, a substance is chlorinated which can be a lower aliphatic hydrocarbon with 1 to 4 carbon atoms and / or a partially chlorinated lower aliphatic hydrocarbon with 1 to 4 carbon atoms. During the reaction, elemental Ghl.or and / or HGl are introduced into the fluidized bed of the Oxyehlorierungs ^ _cv metal halide catalyst particles, and; Oxygen is fed into the bed along with the hydrocarbons and chlorine or HCl. The gaseous reaction products are withdrawn from the upper part, the fluidized bed. During the reaction, the flow rate of the chlorinating agent, oxygen and hydrocarbon and / or chlorocarbon hydrogen, which are passed into the reaction layer, is kept high enough to suspend the catalyst particles and create a dynamic or fluidized layer within the reaction zone. In this type of process, hydrocarbons such as methane, ethane, propane, ethylene and chlorinated hydrocarbons such as 1,2-dichloroethane, tetrachloroethane, methylchloride, chloroform and other similar substances easily become chlorinated hydrocarbons

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respectively converted to higher chlorohydrocarbons. When these reactions are carried out, elemental oxygen or oxygen-containing grasses become like s.B. Air, used according to Wuneoh. With aliphatic Hydrocarbons, such as ethane or methane, use air, albeit large ones Amounts of inert substances contained in the air are taken into account in the recovery system of the process Need to become. You amount of oxygen that at according to an oxychlorination reaction layer or zone the present invention is used, the stoichiometrically determined amount that is required the total HOl contained in the zone to water and elemental chlorine according to the following equation

2H01 + 1/2 O ₂ -J. H ₂ O + Cl ₂

to oxidize.

The temperature of the fluidized bed reaction zones can vary widely depending on the practice and methods of the present invention and depends, to some extent, on the particular hydrocarbon and / or chlorinated hydrocarbon being introduced into the reaction zone. In general, heating temperatures between 260 and 565 ° lead to the most favorable results for most aliphatic hydrocarbons and their partially chlorinated derivatives. Generally speaking, unsaturated hydrocarbons tend to react at lower temperatures than saturated hydrocarbons and this can be taken into account in determining the optimum temperature conditions to be used within that specific reaction zone or fluidized bed. In the oxychlorination of ethylene to 1,2-Dichioräthan a temperature range from 260 ° to ⁰ O 34-3 can for example advantageously: to be applied. In the oxychlorination of 1,2-

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Dichloroethylene and Triohloräthylen, the typical (temperature range sswischen 371 ° and 593 ⁰ O. The contact time, ie the residence time during which the supplied fuel in the reactor can vary widely during the oxy chlorination reaction. Reaction contact times Sound 2 to 25 seconds or longer can if may be used, the gaseous substances typically remaining in the reaction zone for a period of from 2 to 15 seconds.

Because OxyChlorinations that occur in fluidized beds are carried out, lead to exothermic reactions, the layer must be cooled in some way, so that an effective temperature regulation is achieved in the conversion taking place therein. Such Regulation can easily be achieved by appropriate jacketing of the reactors, by interfering with coolants can be achieved in the reaction zone or introduction of cooling coils in the reaction layers. Bayonet cooler can also be used, and other similar heat exchange devices such as expediently in connection with a fluidized bed reactor can be used either alone or in combination. Effective use such a heat exchange device allows the reaction temperature to be easily regulated s that take place in the fluidized bed according to the invention.

The catalysts used for the oxychlorinations described above are appropriately known oxychlorination catalysts or catalysts of the Deacon type, with which suitable Carrier or documents are soaked. Catalysts of this type are usually metal halides, preferably Chlorides of a polyvalent metal, v / ie e.g. copper, iron, chromium, etc. These metal halides, especially in the form of chlorides,

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or can be used with other metals such as alkali metal chlorides and / or alkaline earth metal chlorides or mixtures thereof. In general, any effective metal halide catalyst will of the Deacon type in a satisfactory manner with the gaseous reactants, which in the oxychlorination zone are introduced to produce chlorinated hydrocarbons, which are particularly effective The catalyst for this type of conversion is a mixed catalyst made from copper chloride and potassium chloride. This Catalyst works particularly well when the reactions are carried out at elevated temperatures, i.e. at temperatures between 288 ° and 499 ° C. £ in other The effective catalyst for this reaction is a mixed catalyst made from copper chloride, zinc chloride and calcium chloride. In any event, the preferred catalyst is a catalyst containing a substantial amount of copper chloride contains. A substantial amount of copper chloride is understood to mean catalyst particles which are approximately Contains 2 to 20 wt .- # copper.

Various carriers can be used in carrying out these reactions, and materials such as e.g. silica, clay, fuller's crust, kieselguhr, pumice and other similar substances were used. The choice of the respective type of carrier depends to a large extent on the turbulence of the layer, the speed of the Gases, the permissible quantities of combustion substances and similar considerations. Since abrasion losses are particularly undesirable in fluidized bed processes Florex is a particularly effective catalyst carrier in »fluidized beds (a treated Fuller's earth, which is produced by manufactured by the Floridin Corporation).

The particular method used to apply the catalyst to the support is available one free, however, it is preferred that the method used is that for the most uniform distribution of the catalyst on the carrier. For example

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can easily convert carrier substances into solutions that catalyti See components contained, be immersed and the water of the solution can up from the carrier particles evaporated to remove the solvent from these particles. If desired, the catalytic Substance to be sprayed onto the particles, and mixing devices such as rotary drums, ribbon mixers and the like can be used. Am another effective method of waterproofing Catalytic carrier particles consist of spraying a solution in which the catalyst has been removed a fluidized bed of carrier particles. During the fluidization and impregnation of the carrier particles heat is supplied to the fluidized bed by means of hot inert gases to remove the water of solution from the same to evaporate, leaving a fluidized bed of carrier particles uniform with that to be used catalytic substance are impregnated. Indirect heat exchange with cooling jackets or cooling coils can also be used.

In connection with the use of fluidized beds according to the methods described above can reduce the amount of organic substances that are oxidized or burned during the reaction Use of substantial amounts of inert particles, such as sand, in these layers is reduced will. In general, the dilution by means of sand dividing is used in the fluidized catalytic Layer so barked that the catalytic layer Contains no more than 50 vol. # sand or other inert diluents. The use of thinners can reduce combustion considerably, but it is obvious that the Use of fluidized beds even without such diluents can be made in accordance with the present invention.

The fluidized bed processes according to the invention can operate under conditions such as atmospheric pressure or

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if desired, can be carried out under considerable pressure. Where appropriate, oxychlorination reactions can be carried out in a fluidized bed under pressure to thereby result in improved productivity. Typical pressures between 0.35 and 4.2 kg / cm or higher can be used with no adverse effect on conversions.

The reaction products obtained in the fluidized bed process of the type described above are collected in the upper part of the fluidized bed. Usually the upward flowing gas stream serves to to drive off the reaction products together with unreacted inert components. The reaction products The processes consist of various chlorinated hydrocarbon derivatives in the reaction zone introduced hydrocarbon and / or chlorinated hydrocarbon. Typically the products are collected by condensing and / or absorbing them and after purifying and removing the yeast by conventional methods, the desired organic chlorinated hydrocarbon products of each other by fractional distillation, selective absorption and desorption and other similar separation processes separated.

It has been found that in fluidized bed processes in which oxychlorination reactions are carried out, temperature drops across the bed take place to a greater or lesser extent depending on the effectiveness of the cooling system and the height of the bed. In processes of this type, it has typically been found that a temperature gradient of 30 ^° C. from the top of the layer to the bottom of the layer is not uncommon, although the typical temperature drop varies between 15 and 20 ° C. In carrying out oxychlorination reactions of the type described above, it has been found that the hottest part of the layer is the part immediately above the distributor plate, ie at the

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Place immediately above the point of introduction of the chlorinating agent and the hydrocarbon lies. According to the methods of the present invention, the advantage of this hot zone is used to provide a serve two purposes. When the oxygen is introduced into the reaction zone through pipes or conduits which are arranged in the lower part of the reactor and these lines make the distributor plate at right angles pierce in the vertical direction so that the pipes or lines carry the oxygen into the oxygen ring or lead distributor, which is arranged at the top of the fluidized bed, the oxygen flows through the extremely hot zone of the reaction zone. When flowing through this zone, there is an exchange of heat between the gases and the particles located in this area of the reaction zone, the oxygen flow give a substantial amount of heat. A considerable amount of heat is generated from this part derived from the zone, creating a temperature equilibrium in this part of the reaction zone with temperatures takes place, which predominate in the upper part of the reaction zone.

For a more complete understanding of the present invention, reference is made to the accompanying drawings Drawings, particularly to Figs. 1 and 2, showing a reactor generally designated as 1 and which consists of a shell 2 which surrounds a plurality of individual reaction tubes 3. The reactor tubes 3 are located in two tube sockets, one of which is in the lower part of the reactor and is indicated by 4, and the other is located in the upper part of the reactor and is indicated by 5. Every single one Reactor tube is provided with a bottom piece 6, which is described in detail in Pig. 2 is shown. The upper part of the reactor has a cover 7. The shell 2 is the same with a bent part 8 in the upper part provided so that the circulating heat exchange medium evaporate and out of the system through lines 9 and

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9 running on suitable condensing devices where it is condensed and fed back into the system through the lines 11. The flanges 12 are attached to the lower part of the individual tubes 3 in order to connect the lower parts 6 thereto and to ensure precise alignment of the tubes within the shell 2.

In Figures 2, 3 and 4, the foot piece is composed of a flange part 13 in the upper Part and the shell area 14. Between the flange and the shell part 14 at a certain distance from the lower part of the shell part 14 there is a distributor plate 16. As can be seen more clearly from FIG. the distributor plate 16 has a plurality of holes 17 which are drilled so that the in the wind chamber 18 of the bottom piece into the reactor tube 3 located above the bottom piece can flow in. Running transversely through the chamber 18 of the bottom piece is a tube 19, the one Has a fork, from which a branch 21 rises vertically and the other branch 22 parallel to the chamber 18 crossed to the distribution chamber. The branch 22 is connected to a second vertical branch 24 by a coupling piece 25 and the branches 21 and 24 rise vertically to end at a ring piece 26 which is located inside the reactor tube 3. The ring piece 26 is shown in more detail in Fig. 4 and is provided with a plurality of holes not shown here are provided, which lead the gases from the ring part into the fluidized bed itself. Central in the bottom piece there is a large tube 29 »which is attached to the bottom part with a flange part 30. This tube 29 is of a second tube 31 which is located outside the chamber 18 is cut. Bs is also with attached to a flange 32. This tube 31 is used to remove catalyst materials from the individual Tubes 3 used. A third tube 35, which is fastened to the bottom part with a flange 36, is located in the

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lower part of the bottom piece 6 and protrudes slightly into the chamber 18. This gas supply piece 35 and the Tubes 29 and 19 are preferably spot welded at this point to ensure that they are firmly in place in the To hold floor piece.

In Fig. 1, the upper part of the reactor shows the cover 7, which is provided with a plurality of openings to which various pipes are connected. The pipe 4-1 is a pipe for gas sampling,

^! which is let into the lid and ends in the steam space above the individual pipe parts. The outlet pipe 4-2 is located in the middle part of the lid of the reactor and is used to recover the gases from the chamber. A large tube 43 is located in the upper part of the reaction vessel and is flanged to allow the insertion of a disk so that the reactor can be regulated for processes at given pressures and an appropriate warning is given if the pressure is within the Reaction vessel becomes excessively high. Another tube 4-7 is located in the upper part of the reaction chamber. To the side of the reactor is a pipe 4-9, which is used to recycle the catalyst materials that have collected in the cyclo-separators outside the reactor. This opening and the pipe 4-9 connected to it are also used as a catalyst feed device and also for the introduction of cover gases when pressures are to be exerted on the reactor, for example by creating a nitrogen atmosphere.

When operating the in Figures 1, 2, 3 and 4 The reactor shown is elemental oxygen through the tube 19 and through the tubes 21, 22 and 24- in the Gas distributor ring 26 out. The chlorinating agent, which is made up of either elemental chlorine or HOl or a Mixture of the two is introduced into the reaction zone through the bore 35. Together with the

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Chlorinating agent, the hydrocarbon or onlorocarbon is used as the feed gas. As a typical example of oxychlorination of ethylene, HCl and ethylene are fed in through pipe 35. Elemental oxygen is supplied through the pipe 19 and from there passed on to the oxygen ring 26 through the pipes 21 and 24. Before the gases are fed in, the Realctor tubes 3 are filled to a height of about 3 »30 m with a catalyst consisting of copper chloride and potassium chloride, which is impregnated on Florex particles. The Florex particles pass through a sieve with 108 to 576 meshes / cm and containing 7.3 ^ potassium, 10 to give i "of copper and a sufficient amount of chloride ions to a satisfactory composition of cupric chloride and potassium chloride. The gases are supplied at a rate sufficient to create a fluidization of these catalyst particles. A gas flow of 15 cm / sec. linear velocity is typically sufficient to accomplish this purpose. Ortho-dichlorobenzene circulates in the enveloping part 2 and is brought to the boil therein. The ortho-dichlorobenzene vapors are removed from the system through the expanded area of the jacket and passed through pipes 9 and 9, where they are led to the outer condenser systems, condensed there and then as liquids through pipes 11 and 11, which are in the lower part of the reactor are to be returned to the jacket. When carrying out the reaction, the cold oxygen gas, which is passed through the tubes 21 and 24 into the oxygen ring 26, is heated by the gases and the catalyst particles located in the tube 3 and around the tubes 21 and 24. The oxygen-containing gases that flow out of the oxygen ring when they get into the layer are preheated to such an extent that they approach the reaction temperatures. The hydrocarbon and / or chlorinated hydrocarbon and chlorinating agent flowing upward from the manifold plate 16 contact the heated one

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Oxygen at or near ring 26 and oxychlorination takes place around in this case To give ethylene dichloride which is removed through pipe 42 in the top of the reactor. After removal the 1,2-dichloroethane is from the reaction zone in a vaporous state and is condensed to a liquid outside the reaction zone. The water formed during the reaction is also removed and any water present excess oil is also removed. The product is distilled or otherwise treated to rid it of other chlorinated hydrocarbons and to give purified 1,2-dichloroethane.

It is obvious that this system works in a similar way when substances other than Feed gases are used and products other than chlorinated hydrocarbons are desired. Materials, such as 1,2-dichloroethane, butane, propane, ethane, methane together with the chlorinating agent, which consists of either HCl, chlorine or a mixture thereof, through the pipes 35 into the wind chamber are fed. From there this oasis reaches the reaction zone, through the one in the distributor plate 16 openings located at the foot of each individual reactor tube. The oxygen or the Oxygen in the form of air or «oxygenated Air is passed through the tubes 21 and 24 through the oxygen ring 26. These pipes go up vertically through the reaction vessel 3 itself and are subject to a considerable supply of heat, since this part of the reaction vessel tends to be hotter than the upper parts.

The following examples serve to illustrate various reactions that take place in fluidized bed reactors can be carried out in which the described in situ oxygen preheating system is used got. These embodiments are only

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typical reactions that can take place and the invention is not intended to be limited thereto.

Example 1;

A reaction vessel similar to that in FIG. 1 and having an inner diameter of 2.90 m contains 19 tubes with an inner diameter of 39.4 cm, which are fastened in the reaction vessel in two rows, one on the lower part and one on the upper part . The reactor tubes terminate in an expanded chamber in the upper part of the reaction vessel. The inner diameter of the entire reaction vessel is determined by the shell surrounding it, which has an extensive upper area with an outer diameter of 3.75 m. Each of the individual 19 tubes, which are arranged in the steam vessel, is provided with a head piece, as shown in FIG. Ethylene, HGl and oxygen are fed through this head piece into the reaction vessels. A catalyst is typically prepared by dissolving 13.2 kg of 0uCl ₂ .2H ₂ 0 and 6.9 kg of KGl in 17.6 l of distilled water. This catalyst solution is then applied to Florex particles, which pass through a 108 to 576 mesh / cm sieve, by dripping this solution onto the fluidized Florex particles, which are located in a reactor with an internal diameter of 25 cm, with warm air flowing through the lieactor with a linear surface speed of 17 cm / sec. is blown. The temperature of the bed is maintained at 104 ⁰ G during this dropwise application of the catalyst until the entire 17.6 1 of solution were added. The individual reactor tubes used in these reactors are filled with the catalyst produced in this way up to a height of 3.30 m. A molar ratio of ethylene to HOl to oxygen of 1: 2.03: 0.61 is used and the catalysts in the individual reactor tubes are whirled up. During the fluidization, the layers in the individual tubes prepare to the point

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in which the tubes are filled to the top of the layer, which is the case slightly above the top of the tube. The linear surface velocity of the gases flowing into these reactor tubes is 15 cm / sec. The jacket surrounding all 19 tubes contains circulating ortho-dichlorobenzene and is regulated by pressure cushions so that the reactor tubes are kept ^{at 288 0 O.} When operating the reaction vessel according to this method, HCl and ethylene are in the wind chamber 18 according to the fig. 2 and pass through the openings 17, which are contained in the distributor plate 16, into the catalyst layer, which is contained in the individual tubes 3. The oxygen flows through the lines 21 and 24 into the oxygen ring 26 and is ^{preheated to a temperature of 232 0} O in the process. After flowing out of the openings in the oxygen ring 26, the oxygen contacts the ascending gas stream containing the chlorinating agent and hydrocarbons, ie ethylene and HCl, the reaction taking place instantaneously. The ethylene dichloride thus formed is removed from the vapor region of the reactor through opening 42 located in the central cover piece and condensed to give a liquid ethylene dichloride product. A typical utilization in this process, based on ethylene, is 93 liters or more. The HOI utilization is typically 90-95 fi. The 1,2-dichloroethane yields, based on the ethylene supply, are 89 to 92

Example 2:

Using the system shown in Example 1 and the catalyst described there Perchlorethylene and trichlorethylene obtained by by passing elemental oxygen through ring 26 and 1,2-dichloroethane and HOl into the reaction zones

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the line 35 and the manifold plate 16 introduces. As in Example 1, the oxygen introduced into the oxygen ring passes in the vertical direction through the tubes 21 and 24 and thus through the hot part of the fluidized layer. During its flow, it is preheated to a temperature sufficient to allow an instantaneous reaction to take place when the oxygen from the ring 26 escapes. The temperature is maintained during this process at between 399 ° C and 454- ^0. The trichlorethylene and perchlorethylene, which is produced when the oxygen comes into contact with ethylene dichloride and HCl rising up from the distributor plate, is removed from the top of the reaction vessel through port 42 and is condensed and separated to form a pure trichlorethylene and to give a pure perchlorethylene product. Typical utilizations in a process of this type, based on the 1,2-dichloroethane supplied, are 85 fi. Typical utilization of the chlorinating agent is 80 %. The Gresamtproduktivität of the system, based on the molar basis, is 75 1 ° trichlorethylene and perchlorethylene per mole of 1,2-dichloroethane, which has been supplied.

Example 3:

Using the device described in Example 1 and the catalyst described there Tests are carried out in which ethane and chlorine are introduced into the wind chamber 18 through the pipe 35 and from there passes through the distributor plate 16 into the layer of catalyst particles. Oxygen in the form of air is released through the oxygen ring inserted through tubes 21 and 24. The molar ratio of ethane to chlorine to air that is applied is 1: 1 »4.98. The temperature is adjusted to about 499 ° C in this process, so that a

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chlorinated product is obtained which contains predominantly vinyl chloride. Typical utilizations in this process are 92 $> ethane, 90.7 # chlorine, and the percent vinyl chloride yield is 35 mole percent.

Example 4:

Using the device described in Example 1 and the catalyst specified there, methane and HCl are passed through the pipe 35 into the wind chamber 18 and from there through the gas distribution plate 16 into the individual reactors for the fluidized bed 3. Oxygen in the form of air is fed into the system through tubes 21 and 24 and through oxygen ring 26. The temperature of the reaction vessel is kept at 450 to 518 ^° C. by boiling Dowtherm and a product is obtained which mainly contains carbon tetrachloride and chloroform. The HCl utilization in this system is typically 90+.

Example 5 t

Using the system shown in FIGS. 1 to 4 and the catalyst according to Example 1, a reaction for the production of chlorinated G 1 hydrocarbons is carried out, in which propane and chlorine are passed through the pipe 35 into the wind chamber 18. These gases pass through the wind chamber 18 to the distributor plate 16 and from there into the catalyst layer. Oxygen is introduced in the form of air through tubes 21 and 24 into the oxygen ring 26 where contact with the upwardly flowing gas stream containing propane and HCl takes place. The molar ratio of the materials supplied is 1: 0.33: 2.91 for propane t chlorine: air. The temperature is maintained between 546 and 554 ° C. A large number of chlorinated Cj-hydrocarbons are

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ORIGINAL INSPECTED

hold and run out of the system. The utilization of the system, based on the amount of chlorinated hydrocarbons obtained on the basis of the propane fed, is typically 36 $>. The ear utilization was typically 75 #. The chlorine effectiveness was determined on the basis of the chlorine which was determined in the substance flowing out of the reactor and which was related to the chlorine supplied.

It will be apparent to those skilled in the art that many modifications have been made to this process can be without departing from the basic idea of the invention. For example, different C - ^ - j Og-, C ~ - and ^ -hydrocarbons and chlorinated ones Derivatives of these hydrocarbons in the reaction zone along with chlorine or HCl or mixtures of HCl and elemental chlorine are introduced. Elemental chlorine can be used as the chlorinating agent, but it can also HCl or mixtures of these two substances can be used according to the method given in U.S. Patent No. 2,953,714 Description should be used. Oxygen can be used alone as a building material, however Mixtures of oxygen with air or air itself can also be used.

When carrying out the method according to the invention, it is important to take precautions meet to get the oxygen in preheating the reactor layer and at the same time removing a certain amount of Y / poor from the reaction zone, so that the temperature conditions in the layer are balanced. When working in the above-described In this way, both results can be achieved and oxychlorinations can reduce the Difficulties are carried out to a minimum. The oxygen introduced into the ring system described can be introduced upwards or laterally,

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however, it is preferably inserted at a downwardly sloping angle so that it is at least at weak countercurrent to the chlorinating agent and the fed organics flows when it gets into the layer.

The present invention has been made with reference to certain specific examples and illustrated s forms, but it is not intended to that it is limited thereto unless so indicated in the appended claims brought.

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Claims (4)

Patent claims: Process for the oxychlorination of aliphatic Hydrocarbons and their incompletely chlorinated Derivatives in a fluidized bed of catalyst particles, in which the substance to be chlorinated is mixed with oxygen and a chlorinating agent, which can be elemental chlorine, HCl or a mixture of these substances, is brought into contact, characterized in that the oxygen is introduced into the layer at one point which is substantially above the point of introduction of the chlorinating agent and that to be chlorinated Substance lies in the fact that the oxygen is preheated as it passes through the catalyst layer, that it passes through the fluidized layer of catalyst particles before it comes into contact with the one to be chlorinated Substance and the chlorinating agent is guided along a distance that is sufficient to remove the oxygen in front of the bring said contact to a temperature that is at least 55 ° C below the reaction temperature, that the hydrocarbon is oxychlorinated on contact with the oxygen and the reaction product through an upper part of the layer is peeled off. 2. The method according to claim 1, characterized in that the starting material is aliphatic hydrocarbon with 1-4 carbon atoms is used. 3. The method according to claim 1, characterized in that for the production of 1,2-dichloroethane 909815/1181 146880 ^ Ethylene is used as the starting material. 4. The method according to claim 1, characterized in that for the production of trichlorethylene and Perchlorethylene as the starting material 1,2-dichloroethane is used. For Pittsburgh Plate Glass Company Lawyer 9098 15/1181