DE10251391A1 - Production of ethylenically unsaturated halogen containing aliphatic hydrocarbons by thermal cleavage comprises use of a reactor having a catalyst on and/or in a gas permeable support having an inlet for a flushing gas - Google Patents

Abstract

A process for the production of ethylenically unsaturated halogen containing aliphatic hydrocarbons by thermal cleavage of saturated halogen containing aliphatic hydrocarbon comprises use of a reactor having at least one catalytically active metal on and/or in a gas permeable support having an inlet for a flushing gas. A process for the production of ethylenically unsaturated halogen containing aliphatic hydrocarbons (I) by thermal cleavage of saturated halogen containing aliphatic hydrocarbon (II) comprises: (a) introduction of a reactant gas stream comprising heated gaseous hydrocarbon (II) into a reactor (R) containing at least one catalytically active metal on and/or in a gas permeable support having an inlet for a flushing gas and; (b) adjustment of a pressure and temperature in the reactor such that the product hydrocarbon (I) is formed from the reactant hydrocarbon (II) by thermal cleavage. An Independent claim is included for a reactor (R) comprising an inlet for the reactant hydrocarbon (II), the catalytically active metal and support, an inlet to the catalyst for a gaseous reactant for regeneration of the metal, heating for the gaseous reductant, heating for the gas stream to the reactor and an outlet for the product gas stream (I).

Description

The present invention relates to a process for the production of unsaturated halogenated hydrocarbons from saturated halogenated hydrocarbons and one for carrying out the Device particularly suitable for the method. A preferred method relates to the production of vinyl chloride (hereinafter also referred to as "VC") 1,2-dichloroethane (hereinafter also referred to as "DCE").

The incomplete thermal fission of DCE VC production has been carried out on an industrial scale for many years. there are cracking furnaces used, where the DCE at furnace inlet pressures of 0.8 to 4 MPa and at temperatures from 450 to 550 ° C is partially split into VC and hydrogen chloride. typical cleavage conversions are about 55 mol% of the DCE used.

The process requires considerable amounts of energy for the various process steps, such as heating the DCE to the gap temperature, the reaction itself and the subsequent purification of the product mixture. A group of measures to improve the economics of the process is aimed at energy recovery, for example in the EP-B-276.775 . EP-A-264.065 and DE-A-36 30 162 proposed.

The cracking furnaces are operated continuously. Another improvement in the economics of the process could consist of one if possible long uninterrupted operation of the system. It has However, it has been shown that there are decomposition products on the reactor walls of such plants deposit (coking or coke formation) from time to time Make interruption of continuous operation necessary.

W. Zychlinsky and I. Mielke describe in Chemie Ingenieur Technik 67, 10/95 p.1346-9 (1995) like coke formation in DCE pyrolysis using Fe-II chloride being affected. It was also found that one in the Reactor introduced specimens made of steel increases the sales of the pyrolysis reaction in the short term.

With the present invention provided a method that one compared to conventional Procedures prolonged continuous operation of a cracking furnace permitted.

Another task of the present Invention is the provision of a pyrolysis process of halogen-containing aliphatic hydrocarbons with which compared to conventional Procedures with otherwise the same operating temperature larger sales are possible or with the same in comparison to conventional methods sales a lowering of the operating temperature is possible.

The present invention relates to a process for the production of ethylenically unsaturated halogen-containing aliphatic Hydrocarbons by thermal splitting of saturated halogen-containing aliphatic hydrocarbons comprising the measures:

• a) introducing a feed gas stream containing heated gaseous halogen-containing aliphatic hydrocarbon in a reactor, the inside of at least one arranged on and / or in a gas-permeable carrier has catalytically active metal, and
• b) Setting such a pressure and such a temperature inside the reactor, so that by thermal cleavage of the halogen-containing aliphatic Hydrocarbon hydrogen halide and ethylenically unsaturated halogen-containing aliphatic hydrocarbon are formed.

The method according to the invention becomes an example described on the DCE / VC system. It is also suitable for manufacturing other halogenated unsaturated Hydrocarbons from halogenated saturated hydrocarbons. All these reactions have in common that the cleavage is a radical chain reaction represents, in addition to the desired Product unwanted By-products are formed that coke during continuous operation of the facilities.

The production of Vinyl chloride from 1,2-dichloroethane.

Can be used as a catalytically active metal Virtually any metal that is used in the reactor prevailing reaction conditions is stable, for example not melts. It is believed that metallic surfaces and / or metal halides formed in the cleavage reaction the activation energy lower one or more steps of the radical chain reaction and thereby accelerate the reaction.

Is preferred as catalytically active Metal a metal or a metal alloy from the 8th subgroup the periodic table of the elements, especially iron, cobalt, nickel, Rhodium, ruthenium, palladium or platinum.

Rhodium, ruthenium, Palladium and platinum.

Anyone skilled in the art can be considered as gas-permeable carrier known carrier use. It can be a cage or a floor, for example from a grille or a perforated metal plate is formed, which take up a metal bed and by one Flows through gas can be.

Furthermore, the gas-permeable carrier can be a gas permeable Plate that is made of a flat structure, like a wire mesh, is surrounded by catalytically active metal.

The gas-permeable carrier is preferably a porous molded body. This can consist of the catalytically active metal. It is preferably a porous one Ceramic, which is coated in particular with the catalytically active metal; or it is a porous ceramic that is doped with the catalytically active metal.

The catalytically active metal can be attached in any form in or on the gas-permeable support. The specialist Such arrangements are known.

For example, this can be catalytic active metal in the form of moldings with a possible large surface-to-volume ratio. The catalytically active metal is preferably used as a coating and / or applied as doping on or in the gas-permeable carrier.

For maintaining one if possible Long service life requires the catalytic activity of the metal preferably to get long and / or during restore or regenerate the continued operation of the reactor to be able to.

It has been found that this by rinsing the catalytic surface with a gaseous Reducing agent can be achieved.

Can be used as a gaseous reducing agent all gaseous reducing agents at the temperatures prevailing in the reactor for coke precursors and / or use coking products. The preferred example of this is hydrogen or a mixture of hydrogen with inert gas.

The supply of the gaseous reducing agent takes place via the gas permeable carrier and is fed through this to the catalytically active metal.

In a preferred variant of the inventive method becomes a catalytically arranged on and / or in the gas-permeable carrier active metal with a gaseous reducing agent supplied through the gas-permeable carrier, preferably with hydrogen or with a mixture of hydrogen and inert gas, rinsed.

This can be done with the gaseous reducing agent take place continuously or at predetermined time intervals.

The following process variants offer to:

• - undiluted reducing agent is passed continuously or discontinuously through the gas-permeable support;
• - With Diluted inert gas Reducing agent is continuously or discontinuously the gas permeable carrier passed;
• - the gas permeable carrier is alternately with inert gas and undiluted or diluted with inert gas reducing agent flushed.

The gaseous reducing agent can undiluted or together with inert gases, such as nitrogen and / or noble gases, supplied become.

The temperature of the gaseous reducing agent will be convenient adapted to the temperature prevailing inside the reactor at the location of the gas-permeable support. This can be done, for example, by one installed outside the reactor Heater done.

Through a continuous or intermittent feed of the gaseous Reducing agent leaves the coking of the catalyst surface is efficiently prevented or slow down and thereby extend the operating time of the cracking furnace as well as the Increase sales of the cleavage reaction. At the flushing the operation of the reactor is not interrupted.

Preferably there is at least one a catalytically arranged on and / or in a gas-permeable carrier active metal nearby the entry of the feed gas stream into the reactor. This will already a high concentration when the reactant gas enters the reactor formed on radicals that contribute to an efficient course of the chain reaction.

In a preferred variant of the inventive method the feed gas stream comes in one or more as it passes through the reactor Porous candles Ceramic in touch, on their surface there is in each case a catalytically active metal layer and / or which is doped with catalytically active metal. The candles are preferably with a heating device, for example with a heating cartridge installed inside, equipped and permitted heating the gaseous reducing agent before contact with the catalytically active metal.

That is very particularly preferred Number of candles in the first third of the reactor greater than in the second third and / or in the third third.

The method according to the invention can be used the usual Pressures and / or temperatures are operated. Common operating pressures are in the range of 0.8 to 4 MPa (furnace inlet); common operating temperatures are in the range of 450 to 550 ° C (Furnace exit) and in the range of 250 to 350 ° C (furnace entrance). The endothermic Split reaction needed a constant Supply of energy; this takes place at the passage of the one to be split Gas through the reactor.

With the method according to the invention is a lowering of the usual Operating temperatures possible. This enables a more economical procedure.

Another embodiment of the method according to the invention relates to the thermal cracking of the product gas in a downstream of the reactor adiabatic post-reactor comprising the measures:

• c) introducing the product gas stream containing heated halogen-containing aliphatic hydrocarbon, hydrogen halide and ethylenically unsaturated halogen-containing aliphatic hydrocarbon from the reactor into an adiabatic post-reactor, in which the reaction takes advantage of that supplied by the product gas stream Heat is continued while cooling the product gas, and which preferably has at least one catalytically active metal arranged on and / or in a gas-permeable carrier, and
• d) rinsing if necessary the catalytically active metal with a gaseous reducing agent supplied through the gas-permeable carrier, preferably with hydrogen.

The method according to the invention can only the measures c) and d) include in the adiabatic post-reactor, without an upstream Reactor is used, which is arranged inside on and / or in a gas-permeable carrier has catalytically active metal.

However, the method according to the invention is preferred with the measures c) and d) in the adiabatic post-reactor combined with the use of a upstream reactor, the inside of at least one on and / or arranged in a gas permeable carrier has catalytically active metal.

The invention also relates to a Reactor to carry out of the process defined above comprising the elements:

• i) feed line leading into the reactor for the feed gas stream containing saturated halogen-containing aliphatic hydrocarbon,
• ii) at least one arranged on and / or in a gas-permeable carrier catalytically active metal, which is attached to the inside of the reactor is
• iii) with the gas permeable carrier connected supply line for a gaseous Reducing agent for regenerating the catalytically active metal,
• iv) heater for the gaseous Reducing agent,
• v) heater for heating and / or maintaining the temperature of the Gas flow in the reactor, and
• vi) leading out of the reactor Derivative for the product gas stream of the thermal cleavage containing ethylenic unsaturated halogenated aliphatic hydrocarbon.

The reactor can be used by anyone skilled in the art for such Reactions of known types can be used. A is preferred Tubular reactor.

The gas-permeable carrier is preferably a porous Moldings, especially made of porous ceramics.

In a very preferred embodiment of the reactor according to the invention is the porous Ceramic in the form of a candle, the surface of which with is coated catalytically active metal and / or with catalytically active metal is doped, and the candle is with a lead for the gaseous Reducing agent to regenerate the catalytically active metal fitted. The inside of the Candle a heating device, for example a heating cartridge.

The reactor of the invention can be adiabatic Be post-reactor connected, preferably the ones defined above Contains elements ii), iii) and iv). The heat of reaction required is passed through in the adiabatic post-reactor the warmth of supplied Product gas stream supplied, which cools down.

Instead of the combination of the reactor according to the invention with an adiabatic post-reactor containing elements ii), iii) and iv), such an adiabatic post-reactor can also be used a reactor known per se, the elements ii), iii) and iv) does not have.

A particularly preferred embodiment of the method and the device according to the invention is described below with reference to the 1 and 2 described.

Show it

1 : A preferred gas-permeable support with catalytically active metal arranged thereon shown in longitudinal section

2 : Another preferred gas-permeable support with catalytically active metal arranged thereon shown in longitudinal section

3 : Tubular reactor with support according to 1 or 2 in longitudinal section.

In a particularly preferred variant of the process according to the invention, the feed gas stream comes with one or more devices of the type shown in FIG 1 outlined type in touch, which is described below.

In an outer tube ( 1 ) is by means of two opposite lids or flanges ( 2 ) a cylindrical, porous molded body ( 3 ) clamped on the inside with a catalytically active layer ( 4 ) is provided. The arrangement of the molded body ( 3 ) in the outer tube ( 1 ) become a mantle room ( 5 ) and an interior ( 6 ) formed, the jacket space ( 5 ) on the end faces of the covers or flanges ( 2 ) against the interior ( 6 ) and against the outer tube ( 1 ) is sealed.

Instead of the arrangement of the shaped body generated by the use of lids or flanges ( 3 ) in the outer tube ( 1 ) With a suitable choice of material, the shaped body can also be connected to the outer tube in other ways, for example by screwing and / or welding, so that the jacket space ( 5 ) and interior ( 6 ) in such a way that the jacket space ( 5 ) against the interior ( 6 ) and against the outer tube ( 1 ) is sealed.

Such a device is in 2 shown. A cylindrical, porous and on the inside with a catalytically active layer ( 4 ) provided molded body ( 3 ) has an outer tube on the front ( 1 ) welded. The arrangement of the molded body ( 3 ) in the outer tube ( 1 ) become a Mantle space ( 5 ) and an interior ( 6 ) formed, the jacket space ( 5 ) against the interior ( 6 ) and against the outer tube ( 1 ) is sealed.

The invention also relates to a such device, a reactor for performing the above defined Method comprising at least one such device and a process for the production of ethylenically unsaturated halogen-containing aliphatic Hydrocarbons by thermal splitting of saturated halogen-containing aliphatic hydrocarbons, in which a such device is used.

The hollow body ( 3 ) the same inner diameter or the same free cross-section as the upstream, intermediate or downstream reaction tube.

The cylindrical, porous shaped body ( 3 ) can consist of sintered metal, porous ceramic or another porous and temperature-resistant material. In a particularly preferred variant, the porous hollow body ( 3 ) made of zirconium oxide.

The catalytically active metal layer can be applied to the inside of the porous molded body in various ways e.g. by vapor deposition, sputtering, galvanic or currentless Metal deposition, impregnation, precipitation (Impregnation) or Combinations of these methods.

The type of application of the catalytic active layer is not limited to the methods listed here.

The cylindrical, porous shaped body ( 3 ) can also or additionally be doped with the catalytically active metal.

The sealing of the jacket space ( 5 ) against the interior ( 6 ) by means of a seal ( 7 ) take place, in a preferred embodiment a spring ( 8th ) is worked out from the end face of the cylindrical, porous molded body, which is inserted into the seal ( 7 ) pushes in or cuts in.

The end face or the section of the cylindrical, porous shaped body ( 3 ), if it is made of ceramic material, can be sealed with a so-called glass solder or a temperature-resistant ceramic adhesive.

The sealing of the jacket space ( 5 ) against the outside space is preferably done using seals ( 13 ).

Spacers worked into the face of the cover or flanges ( 9 . 10 . 11 ) ensure a defined surface pressure of the seals ( 8th . 13 . 14 ) and protect the cylindrical, porous molded body ( 3 ) before break.

With the seal ( 7 ) it can be a metal seal or a seal made of another temperature-resistant and sufficiently soft material. A metal seal is preferred.

For the seals ( 13 ) and ( 14 ) are seals made of a temperature-resistant material such as graphite, asbestos or asbestos substitutes. Other temperature-resistant materials can also be used.

For the seals ( 13 ) and ( 14 ) can also be welding lip seals.

For the seals ( 13 ) and ( 14 ) it can also be a combination of an internal seal made of a soft and temperature-resistant material and an external welding lip seal.

If the cylindrical, porous molded body ( 3 ) is a break-resistant material, such as sintered metal, it can also be used with the lids ( 2 ) are screwed or welded.

In such an embodiment, an arrangement is preferred in which the cylindrical, porous shaped body ( 3 ) with one of the covers or flanges ( 2 ) is welded and screwed to the other cover (flange) so that the cylindrical, porous molded body ( 3 ) z. B. can be easily dismantled for cleaning and regeneration purposes.

An arrangement in which at both ends of the cylindrical, porous shaped body ( 3 ), provided that this consists of metallic sintered material, cylindrical connecting parts or intermediate pieces made of solid material of the same inside and outside diameter are welded on, which can be provided with threaded holes for screwing on flanges, for example, or to which the flanges can be welded directly.

On the screwed side, the jacket space is sealed off from the interior by a seal between the cylindrical, porous molded body ( 3 ) and cover or flange ( 2 ) guaranteed.

The device described is the preheated feed gas stream ( 15 ) flows through.

Is the device downstream of a reaction path and if this is operated as an adiabatic post-reactor, it will flows through the reactor outlet gas mixture.

The preheated feed gas ( 15 ) disintegrates, for example by dissociative adsorption, on the catalytically active surface ( 4 ) into radicals, which in turn promote the progress of the radical chain reaction.

The cylindrical, porous shaped body ( 3 ) a gaseous reducing agent, a mixture of gaseous reducing agent and inert gas or an inert gas flows through from outside to inside. For this purpose, the gas mixture) through an inlet opening from the outside through a supply line, not shown, into the jacket space ( 5 ) introduced and flows through the cylindrical, porous molded body ( 3 ) and the catalytically active layer ( 4 ) in the interior ( 6 ) of the device. It understands of itself that molded body ( 3 ) catalytically active layer ( 4 ) must be designed and arranged in such a way that a gas flow as uniform as possible through these layers is made possible and that no zones are formed which are not traversed by gas.

In the 1 and 2 The device shown can be installed in a conventional tube reactor for producing ethylenically unsaturated halogen-containing aliphatic hydrocarbons by thermal cleavage of saturated halogen-containing aliphatic hydrocarbons.

Such installation is in 3 shown schematically.

The tubular reactor comprises an oven as well as a reaction tube.

In general, an oven fired with a primary energy source, such as oil or gas, is placed in a so-called radiation zone ( 16 ) and a convection zone ( 17 ) divided up.

In the radiation zone ( 16 ) the heat required for the pyrolysis is transferred to the reaction tube primarily by radiation from the furnace walls heated by the burner.

In the convection zone ( 17 ) the energy content of the hot flue gases emerging from the radiation zone is used by convective heat transfer. The starting material of the pyrolysis reaction, for example EDC, can thus be preheated, evaporated or overheated. The production of hydrogen, water vapor and / or the preheating of combustion air is also possible.

In a typical arrangement, such as that shown in EP-A-264.065 is shown, liquid EDC is first preheated in the convection zone of the cracking furnace and then evaporated in a special evaporator outside the cracking furnace. The vaporous EDC is then again fed to the convection zone and overheated there, the pyrolysis reaction already being able to start. After overheating, the EDC enters the radiation zone, where the conversion to vinyl chloride and hydrogen chloride takes place.

As a result of the high temperatures prevailing in the radiation zone and in the entrance of the convection zone, it is advantageous to 1 or 2 not to arrange the outlined device directly within these zones, since otherwise, for example, a defined temperature setting of the gas or gas mixture used for the continuous or intermittent regeneration of the catalyst surface is not possible or is possible only with difficulty.

Therefore, an arrangement as shown in 3 is shown schematically.

Here, the cracking furnace is separated by two additional, non-heated compartments ( 18 ) which can be thermally insulated. From the actual radiation or convection zone ( 16 . 17 ) then loops of the reaction tube through these compartments ( 18 ) guided. The devices according to are then in these loops, preferably within the straight length of these loops 1 or 2 ( 19 ) containing catalytically active elements, i.e. installed in the reaction tube, so that the educt gas flow reaction tube and interior ( 6 ) can flow through the device.

The from the radiation or convection zone ( 16 . 17 ) in the unheated compartments ( 18 ) Guided loops of the reaction tube are preferably provided with thermal insulation.

The invention also relates to the use of a catalytically active metal with a regenerable surface the production of ethylenically unsaturated halogen-containing aliphatic Hydrocarbons by thermal splitting of saturated halogenated aliphatic hydrocarbons.

Claims (33)

Process for the production of ethylenically unsaturated Halogenated aliphatic hydrocarbons through thermal Cleavage of saturated halogen-containing aliphatic hydrocarbons comprising the Activities: a) Introducing a feed gas stream containing heated gaseous halogen-containing aliphatic hydrocarbon in a reactor inside at least one catalytically arranged on and / or in a gas-permeable carrier has active metal, and b) Setting such a pressure and such a temperature inside the reactor, so that by thermal Cleavage of the halogen-containing aliphatic hydrocarbon hydrogen halide and ethylenically unsaturated halogen-containing aliphatic hydrocarbon are formed. A method according to claim 1, characterized in that as a saturated Halogen-containing aliphatic hydrocarbon 1,2-dichloroethane used from which vinyl chloride is produced by thermal fission. A method according to claim 1, characterized in that as a catalytically active metal is a metal or a metal alloy from the 8th subgroup of the Periodic Table of the Elements, in particular Rhodium, ruthenium, palladium or platinum is used. A method according to claim 1, characterized in that the catalytically active metal as a layer and / or as a doping on or in the gas permeable Carrier, is preferably formed on and / or in a porous carrier. A method according to claim 1, characterized in that the catalytically active metal arranged on and / or in the gas-permeable carrier is supplied with a gas-permeable carrier led gaseous reducing agent, preferably with hydrogen or a mixture of hydrogen and inert gas, is flushed. A method according to claim 5, characterized in that rinsing with the gaseous Reducing agent continuously or at predetermined time intervals he follows. A method according to claim 1, characterized in that is at least close the entry of the educt gas stream into the reactor and / or in a gas permeable carrier arranged catalytically active metal. A method according to claim 7, characterized in that the educt gas flow during the passage in the reactor with one or more Porous ceramic candles in touch comes on the surface of which each has a catalytically active metal layer and / or which are doped with catalytically active metal. A method according to claim 8, characterized in that the gaseous Reducing agent before contact with the catalytically active metal is heated by a heater installed in the candle. A method according to claim 8, characterized in that the number of candles in the first third of the reactor is larger than in the second third and / or in the third third. A method according to claim 1 for thermal cleavage of the product gas in an adiabatic downstream of the reactor Post reactor comprising the measures: c) Introducing the product gas stream containing heated halogen-containing aliphatic hydrocarbon, hydrogen halide and ethylenic unsaturated halogenated aliphatic hydrocarbon from the reactor in an adiabatic post-reactor in which the reaction is exploited the heat supplied by the product gas stream while cooling the Product gas continued is, and the inside preferably at least one on and / or in a gas permeable carrier arranged arranged catalytically active metal, and d) rinse if necessary the catalytically active metal with a gaseous reducing agent supplied through the gas-permeable carrier, preferably with hydrogen or with a mixture of hydrogen and an inert gas. Process for the production of ethylenically unsaturated Halogenated aliphatic hydrocarbons through thermal Cleavage of saturated halogen-containing aliphatic hydrocarbons comprising the Activities: a) Introducing a feed gas stream containing heated gaseous halogen-containing aliphatic hydrocarbon in a reactor, to trip someone such a pressure and temperature inside the Reactor so that by thermal fission of the halogen-containing aliphatic hydrocarbon hydrogen halide and ethylenic unsaturated halogen-containing aliphatic hydrocarbon are formed, c) Introducing the product gas stream containing heated halogen-containing aliphatic hydrocarbon, hydrogen halide and ethylenic, unsaturated halogenated aliphatic hydrocarbon from the reactor in an adiabatic postreactor downstream of the reactor, in which the reaction takes advantage of that supplied by the product gas stream Warmth under cooling down of the product gas continued is, and the inside arranged at least one on and / or in a gas-permeable carrier has catalytically active metal, and d) if necessary do the washing up the catalytically active metal with a gaseous reducing agent supplied through the gas-permeable carrier, preferably with hydrogen or with a mixture of hydrogen and an inert gas. Reactor for performing the method according to claim 1 comprising the elements: i) feed line leading into the reactor for the Educt gas stream containing saturated halogen-containing aliphatic hydrocarbon, ii) at least a catalytically arranged on and / or in a gas-permeable carrier active metal, which is attached to the inside of the reactor, iii) with the gas permeable carrier connected supply line for a gaseous Reducing agent for regenerating the catalytically active metal, iv) Heater for the gaseous Reducing agent, v) heating device for heating and / or maintenance the temperature of the gas stream in the reactor, and vi) from the reactor premier Derivative for the product gas stream of the thermal cleavage containing ethylenic unsaturated halogenated aliphatic hydrocarbon. Reactor according to claim 13, characterized in that the reactor is a tubular reactor. Reactor according to claim 13, characterized in that the gas permeable carrier from porous Ceramic is made. Reactor according to claim 15, characterized in that the porous ceramic is designed in the form of a candle, the surface of which is coated with catalytically active metal and / or which is doped with catalytically active metal and which has an addition line for the gaseous reducing agent for regenerating the catalytically active metal is equipped. Reactor according to claim 16, characterized in that the candle has a heater inside. Reactor according to claim 13, characterized in that this is followed by an adiabatic post-reactor, which preferably elements ii), iii) and defined in claim 13 iv) contains. Device for introducing a gas into a reactor according to claim 13, comprising an outer tube ( 1 ) in which a gas-permeable carrier in the form of a cylindrical, porous shaped body ( 3 ), which has a catalytically active metal layer on the inside ( 4 ) and / or which is doped with catalytically active metal, is arranged so that a jacket space ( 5 ) and an interior ( 6 ) are formed and the shell space ( 5 ) against the interior ( 6 ) and against the outer tube ( 1 ) is sealed. Apparatus according to claim 19, characterized in that a gas-permeable support in the form of a cylindrical, porous shaped body ( 3 ), which has a catalytically active metal layer on the inside ( 4 ) and / or which is doped with catalytically active metal, by means of two opposing lids or flanges ( 2 ) in an outer tube ( 1 ) is arranged so that a jacket space ( 5 ) and an interior ( 6 ) are formed and that the jacket space ( 5 ) on the end faces of the covers or flanges ( 2 ) against the interior ( 6 ) and against the outer tube ( 1 ) is sealed. Apparatus according to claim 19, characterized in that the cylindrical shaped body ( 3 ) consists of sintered metal, porous ceramic or in particular of zirconium oxide. Device according to claim 20, characterized in that in the end face the cover or flanges ( 2 ) Spacers ( 9 . 10 . 11 ) are incorporated, which ensure a defined surface pressure of the seals ( 8th . 13 . 14 ) ensure and the molded body ( 3 ) protect against breakage. Apparatus according to claim 20, characterized in that for sealing the jacket space ( 5 ) on the end faces of the covers or flanges ( 2 ) against the interior ( 6 ) and against the outer tube ( 1 ) Metal seals are provided. Device according to claim 19, characterized in that the shaped body ( 3 ) consists of sintered metal and is screwed and / or welded to the outer tube. Device according to claim 20, characterized in that the shaped body ( 3 ) consists of sintered metal, which with the lids or flanges ( 2 ) is screwed and / or welded. Device according to claim 25, characterized in that the shaped body ( 3 ) with one of the covers or flanges ( 2 ) is welded and to the other cover or flange ( 2 ) is screwed. Device according to claim 25, characterized in that the shaped body ( 3 ) cylindrical connecting parts or intermediate pieces made of solid material of the same inside and outside diameter are welded onto both ends, which are preferably with threaded holes for screwing on lids or flanges ( 2 ) are provided or to which the covers or flanges ( 2 ) are directly welded on. Reactor according to claim 13, characterized in that it has at least one device according to claim 19, the interior ( 6 ) of the feed gas ( 15 ) is flowed through. Reactor according to claim 28, characterized in that it comprises a furnace and a loop-shaped reaction tube in the furnace, the furnace having a radiation zone ( 16 ), a convection zone ( 17 ) and at least two non-heated compartments ( 18 ) into the loops of the reaction tube from or into the radiation or convection zone ( 16 . 17 ) are performed, the at least one device according to claim 19 being located in at least one compartment ( 18 ) and is installed in the reaction tube so that the educt gas flow reaction tube and interior ( 6 ) can flow through the device. Reactor according to claim 29, characterized in that at least one device according to claim 19 within of straight lengths the loop of the reaction tube is located. Reactor for performing the method according to claim 12, characterized in that the adiabatic downstream of the reactor Post-reactor elements ii), iii) and defined in claim 13 iv) contains. Reactor according to claim 31, characterized in that it has at least one device according to claim 19, the interior ( 6 ) of the feed gas ( 15 ) is flowed through. Use of a catalytically active metal with a regenerable surface in the production of ethylenically unsaturated halogen-containing aliphati shear hydrocarbons by thermal splitting of saturated halogen-containing aliphatic hydrocarbons.