Title of Invention	APPARATUS AND PROCESS FOR OXYCHLORINATION
Abstract	The invention relates to an apparatus (1) and to a process for the oxychlorination of alkenes to chlorinated alkanes using hydrogen chloride and oxygen. The apparatus (1) has gas inlets (4,5,6) into a fluidised bed (12) comprising catalyst particles (13) of a fluidised bed reactor (14) and at least one reaction gas outlet (11) above the fluidised bed (12) as well as a cooling arrangement (15) for the thermal control of an exothermic oxychlorination reaction. A plurality of gas inlets (4,5,6) for the same inlet gases are arranged in vertical distribution along the fluidised bed (12). The cooling arrangement (15) has cooling circuits (16,17,18) arranged vertically one above another which project into the fluidised bed (12). Using the apparatus (1), dichloroethane is prepared on a large industrial scale with optimum use of the starting material ethene.

Title of Invention

APPARATUS AND PROCESS FOR OXYCHLORINATION

Abstract

The invention relates to an apparatus (1) and to a process for the oxychlorination of alkenes to chlorinated alkanes using hydrogen chloride and oxygen. The apparatus (1) has gas inlets (4,5,6) into a fluidised bed (12) comprising catalyst particles (13) of a fluidised bed reactor (14) and at least one reaction gas outlet (11) above the fluidised bed (12) as well as a cooling arrangement (15) for the thermal control of an exothermic oxychlorination reaction. A plurality of gas inlets (4,5,6) for the same inlet gases are arranged in vertical distribution along the fluidised bed (12). The cooling arrangement (15) has cooling circuits (16,17,18) arranged vertically one above another which project into the fluidised bed (12). Using the apparatus (1), dichloroethane is prepared on a large industrial scale with optimum use of the starting material ethene.

Full Text	FORM 2 THE PATENT ACT 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See Section 10, and rule 13 TITLE OF INVENTION APPARATUS AND PROCESS FOR OXYCHLORINATION APPLICANT(S) a) Name : VINNOLIT GMBH & CO. KG b) Nationality : GERMAN Company c) Address : PROFIT-CENTER VINTEC WERK GENDORF 84 504 BURGKIRCHEN GERMANY PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed : - The invention relates to an apparatus and to a process for the oxychlorination of alkenes to chlorinated alkanes using hydrogen chloride and oxygen. For that purpose the apparatus has gas inlets into a fluidised bed comprising catalyst particles of a fluidised bed reactor. In addition, the fluidised bed reactor has at least one reaction gas outlet above the fluidised bed as well as a cooling arrangement for the thermal control of an exothermic oxychlorination reaction. Such an apparatus and a process for the preparation of 1, 2-dichJoroethane is known from the specification DE 40 33 048 A 1. In the known process, an alkene, such as ethene, is reacted by single-stage oxychlorination to form 1,2-dichloroethane, also referred to as "EDC", using hydrogen chloride and oxygen or an oxygen-containing gas such as air, at temperatures of from 200 to 250°C and pressures of from 2 to 6 bar (0.2 MPa to 0.6 MPa), in the presence of a catalyst consisting of copper(II) chloride on carrier particles, in accordance with the following equation: C2H4, + 2HCI + 1/2O2 ↔ CI-CH2-CH2-CI + H2O. The catalyst particles are held in a fluidised bed, as the reaction zone, which is fluidised by a recycle gas, the input gases being introduced into the fluidised bed under pressure via gas inlets. Via a gas outlet above the fluidised bed, the reaction gases, the water and l,2dichloroethane and also unreacted ethene, unreacted oxygen and by-products, such as carbon monoxide, carbon dioxide and residual gases, are discharged and for the most part conveyed in the cycle after liquid 1 ,2-dichloroethane and water have been removed in condensation stages. The gas conveyed in the cycle, composed of by-products and unreacted input gases, is mixed with ethene and conveyed to the reaction zone, that is, the fluidised bed in the lower region of the fluidised bed reactor. The oxygen and the hydrogen chloride gas stream are mixed prior to the reaction zone and are added in an amount that leads to the reaction of the hydrogen chloride in the reaction zone and to the inevitably resulting formation of a small amount of carbon monoxide and carbon dioxide from the ethene fed in. The content of oxygen in the recycle gas is kept so small that a flammable gas mixture is not formed in the cycle. The single-stage process known from the specification DE 40 33 048 A 1 and the apparatus associated therewith have the disadvantage that, if the amount of catalyst is increased in order to increase the productivity of the fluidised bed reactor and in addition increase the EDC production per catalyst amount and time, then there is an over-proportional increase in the oxidation rate of ethene and hence also an over-proportional increase in the by-products such as carbon monoxide and carbon dioxide. Consequently, although a single-stage arrangement is compact and favourable in terms of investment costs, it has the disadvantage of higher ethene losses resulting from oxidation to carbon dioxide and carbon monoxide. Thus, the ethene and oxygen yields, especially, are worsened relative to investment costs as a result of the increase in reactor productivity when there is a simultaneous increase in the capacity of existing single-stage arrangements. Consequent disadvantages are accordingly increased by-product formation and increased operating costs. A further aspect of the invention concerns an improvement in the introduction of gas into the fluidised bed reactor. In that connection, there is known for introducing gas into a fluidised bed reactor, from the specification DE 102 23 789 A 1, a device that has gas inlet pipes which have gas fluidising means upstream from and/or at their discharge orifices. Those means are alleged to bring about a greater fluidisation of the catalyst particles composed of aluminium oxide carriers having a copper(II) chloride coating and to minimise abraded material. In customary fluidised bed plants used on a large industrial scale, abraded material originates as a result of the catalyst particles in the upper region of the oxychlorination reactor being deposited and recovered in a plurality of series-connected cyclones, with the result that the majority of the particles are retained in the reactor. But catalyst dust originates from abraded catalyst both in the cyclones and on the walls of the reactor vessel as well as on the gas inlet pipes, so that the abraded catalyst passes into the reaction gas leaving the reactor and reaches the working up of the 1,2-dichloroethane where it has to be separated off again. The aim of the present invention is therefore to provide an apparatus and a process for the oxychlorination of alkenes to chlorinated alkanes using hydrogen chloride and oxygen. Using the apparatus and the process, preferably 1, 2-dichloroethane is to be prepared on a large industrial scale with the use of commercial oxychlorination catalysts and a high specific catalyst output, wherein the oxidation of ethene to byproducts, such as carbon dioxide, is to be minimised, the starting material yields are to be maximised and EDC is to be yielded with improved purity, especially with an unchanged low level, or reduced level, of abraded catalyst. The aim is achieved by the subject of the independent claims. Advantageous further developments of the invention are disclosed in the dependent claims. According to the invention, an apparatus is provided for the oxychlorination of at least one alkene to at least one chlorinated alkane using hydrogen chloride and oxygen or an oxygencontaining gas, wherein the apparatus has gas inlets into a fluidised bed comprising catalyst particles of a fluidised bed reactor. In addition, the apparatus has at least one reaction gas outlet above the fluidised bed as well as a cooling arrangement for the thermal control of an oxychlorination reaction. In that new apparatus, a plurality of gas inlets are arranged in vertical distribution along the fluidised bed. The cooling arrangement furthermore has cooling circuits arranged vertically one above another which project into the fluidised bed. An advantage of this apparatus is that, as a result of the vertically distributed gas inlets for inlet gases and starting materials, an optimum amount of catalyst with optimum control of the exothermic oxychlorination reaction can be provided, especially since the cooling circuits are also arranged in vertical tiers, one above another, in the fluidised bed. Consequently, the optimum reaction temperature provided hitherto for single-stage processes can be retained and nevertheless the total amount of catalyst located in the reactor, and also the amount of inlet gases, can be increased as desired. This is governed solely by the height of the fluidised bed reactor. Consequently, the advantage of this apparatus over a single-stage oxychlorination apparatus is that optimum conditions for the conversion of ethene can be achieved by feeding hydrogen chloride and oxygen into the vertically divided regions of the fluidised bed with its catalyst regions in tiers one above another. In addition, in a preferred embodiment of the apparatus according to the invention, for feeding in hydrogen chloride and oxygen or oxygen-containing gases, either individually or in the form of a mixture, there are provided at least two tiers of gas inlets arranged in vertical rungs. In those tiered gas inlets it is also possible for optimum shaping of the gas inlet orifices, such as are known from the above-mentioned specification DE 102 23 789 A 1, to be used. That has the advantage that the resulting 1, 2-dichloroethane is charged with a minimum content of catalyst dust. In the apparatus according to the invention the content of catalyst dust can be minimised even further by having a fine-dust filter connected upstream of the reactor gas outlet of the fluidised bed reactor, which filter separates the reaction gases emerging from the reactor and the catalyst dust from one another. In that way, a higher degree of purity of the EDC starting product is advantageously also achieved. In a further preferred embodiment of the apparatus according to the invention, newly designed gas inlets are provided for feeding in inlet gases and feeding in starting materials, which inlets extend over the reactor height, or at least over a portion of the reactor height, of the fluidised bed reactor and have vertical gas distributors. The vertical gas distributors have the outer form of pipes, from the faces of which the inlet gases discharge directly into the fluidised bed region transversely to the main stream. While the circulating stream, which keeps the catalyst particles in fluid motion, flows vertically through the fluidised bed reactor from a bottom side to a top side of the fluidised bed reactor as the main stream of gas, the inlet gases are introduced continuously transversely to the main stream into the fluidised bed along the height of the fluidised bed reactor through the vertical gas distributors. Since the flow vectors of the inlet gases relative to the recycle gas are perpendicular to one another, an optimum introduction of fluidising gas which is extremely gentle for the catalyst particles is achieved. In addition, the vertical gas distributors can have apertures distributed along their length in the form of so-called perforated distributors, it being possible for the cross-section of the apertures to be kept extremely small to strengthen the fluidising action. On the other hand, instead of perforated distributors it is also possible to use rod-shaped gas distributors in the form of vertically arranged pipes formed with open-pored material, the pipes being arranged adjacent to one another in the fluidised bed. As a result of the fine pores of the open-pored material, the reaction gases are able to flow in a uniformly distributed manner, transversely to the main stream of gas, over the height of the reactor or over a portion of the height of the reactor into the fluidised bed comprising catalyst particles. Using such open-pored pipes, for example sintered ceramic pipes, the inlet gas stream is further refined, so that the catalyst particles are gently blended with the inlet gas in the fluidised bed region. In addition, the faces of the vertical pipes are coated with a gas film by the emerging gases, so that mechanical contact with the catalyst particles is reduced, resulting in reduced abrasion of catalyst material in the fluidised bed. Preferably, arrangement is made for the apparatus according to the invention to be provided with gas inlets for feeding in hydrogen chloride and oxygen or oxygen-containing gases either individually or in the form of a mixture over the reactor height or over a portion of the reactor height of the fluidised bed reactor, the hydrogen chloride and/ or the oxygen or the oxygen-containing gases emerging from the vertically arranged perforated distributors or from the fine-pored distributors, which have preferably been produced from sintered metal or sintered ceramics. Unlike the single-stage introduction of inlet gases such as hydrocarbon gas, oxygen and hydrogen chloride known from the prior art, inlet gas is thus, as a result of the vertical distributors, uniformly blended over an extended region of the reactor with an ethene flowing vertically in the main stream. In addition, in a preferred embodiment of the apparatus, an alkene gas feed together with a gas mixture conveyed in the cycle has at least one gas inlet arranged in the lower region of the fluidised bed. That lower gas inlet with recycle gas conveyed in the cycle provides for a main gas stream of ethene and recycle gas from a lower inlet in the lower region of the fluidised bed reactor to an upper outlet in the upper region of the fluidised bed reactor, fine dust being captured to a very large extent by a fine-dust filter arranged in the upper region of the fluidised bed reactor. hi a further preferred embodiment of the apparatus according to the invention, in addition to the lower gas inlet for a gas mixture of ethene and recycle gas, a vertically tiered gas inlet is provided in the region of the fluidised bed. In that embodiment of the apparatus, a portion of the required ethene can be fed into the fluidised bed reactor in the lower region together with the recycle gas, and a further portion of pure ethene can be fed in in a first stage or a plurality of subsequent stages. In that arrangement, a plurality of vertically tiered gas inlets for feeding in alkene gas are arranged vertically one above another. In a further preferred embodiment of the apparatus according to the invention, arrangement is also made for gas inlets to be provided for feeding in solely alkene gas by way of vertical distributors along the reactor height or at least a portion of the reactor height of the fluidised bed reactor. In that arrangement, perforated distributors or fine-pored distributors, preferably of sintered metal or sintered ceramics, are arranged in the apparatus for the alkene gas feed. As a result of that new construction for the introduction of gas via perforated distributors and/or vertical fine-pored distributors, losses of catalyst can also advantageously be further reduced for the multi-stage process according to the invention. For discharging the heat of reaction and hence for the thermal control of the oxychlorination process, there are provided as a cooling arrangement in the novel apparatus at least two cooling pipe bundles arranged vertically one above another. As a result of those cooling pipe bundles arranged vertically one above another, it is possible at any stage of the gas inlet feed for an optimum equilibrium to be achieved between ethene reactions with hydrogen chloride and oxygen, so that the combustion of the ethene by oxygen to by-products such as carbon monoxide and carbon dioxide is kept extremely low. That reduction in oxidation rates for ethene to by-products is surprising, because the reaction temperatures used hitherto in single-stage processes can be retained unchanged, despite increased loading with amounts of catalyst and despite increased loading of the new apparatus with inlet gases and reaction gases. Discharge of the heat of reaction from the cooling pipe bundles can be effected by natural circulation when the cooling pipe bundles are appropriately arranged to allow natural circulation of the cooling medium by the effects of gravity. On the other hand, provision can also be made for the apparatus to be equipped with circulating pumps for the cooling pipe bundles to achieve forced circulation of the cooling medium. A further aspect of the invention concerns a process for the preparation of at least one chlorinated alkane by reaction of at least one alkene with hydrogen chloride and oxygen or an oxygen-containing gas in an oxychlorination reactor to form a reaction gas in a fluidised bed reactor. For that purpose, the hydrogen chloride and oxygen or the oxygen-containing gas are fed into the fluidised bed in vertical distribution along the fluidised bed. As a result of the vertical distribution of the inlet gases hydrogen chloride and oxygen-containing gas or oxygen, the single stage feed, which leads to increased combustion of the ethene to byproducts such as carbon monoxide and carbon dioxide, is avoided. In addition, in a preferred arrangement of the process, the feeding-in of hydrogen chloride and oxygen or oxygen-containing gas can extend over the height of the reactor or over a portion of the height of the reactor and can be effected virtually continuously by fine distribution, preferably by means of perforated distributors or by means of fine-pored distributors. The advantages of the vertically arranged fine-pored distributors having a gas outflow orthogonal to the main direction of the ethene-containing recycle gas have already been discussed hereinabove and will therefore not be explained again here. In addition to that almost continuous feed, the feeding-in of ethene as the alkene together with a gas mixture conveyed in the cycle can be effected in one stage or a plurality of stages. When it is carried out in one stage, the ethene is fed in in the lower region of the fluidised bed furnace. In the case of multi-stage feed, gas inlets for introducing ethene are additionally provided in the middle and upper regions of the fluidised bed. Preference is thus given to a process in which the feeding-in of alkene is effected at one site in a mixture with a gas mixture conveyed in the cycle and, in addition, is effected at at least one further site as pure starting material. On the other hand it is also possible for the alkene to be fed in at one site in a mixture with the gas mixture conveyed in the cycle and for an additional feed-in to be effected virtually continuously over the height of the reactor or over a portion of the height of the reactor by a fine distribution preferably being effected by means of perforated distributors or fine-pored distributors. Such a process not only has the advantage of making optimum use of the ethene to produce 1, 2-dichloroethane but also has the advantage of an appreciable reduction in the abrasion of catalyst to catalyst dust, since the gases flowing out of the vertically arranged distributors transversely to the direction of the main stream form a gas film which protects the catalyst particles against contact with the pipe-shaped vertical distributors and the surfaces thereof. That protective gas film is especially impervious in the case of fine-pored distributors, since the gas stream flows almost continuously. The process is additionally optimised by discharge of the heat of reaction into at least two or more cooling pipe bundles arranged one above another. The heat of reaction can therefore be optimally related to the oxychlorination procedure in the respective stages of the fluidised bed reactor. To that end, discharge of the heat of reaction can be conducted by way of the cooling medium in natural circulation, or can be effected by forced circulation by using a circulating pump. The invention will now be explained in detail in relation to the apparatus, with reference to the accompanying Figures. Figure 1 is a diagrammatic drawing of a fluidised bed reactor of an apparatus according to a first embodiment of the invention; Figure 2 is a diagrammatic drawing of a fluidised bed reactor of an apparatus according to a second embodiment of the invention; Figure 3 is a diagrammatic drawing of a fluidised bed reactor of an apparatus according to a third embodiment of the invention; Figure 4 shows a cut-away portion, on an enlarged scale, of the vertical distributor systems according to the apparatus of the third embodiment of the invention shown in Figure 3. Figure 1 is a diagrammatic drawing of a fluidised bed reactor 14 of an apparatus 1 according to a first embodiment of the invention. The fluidised bed reactor 14 has a pressure-resistant vessel 28 having a pressure resistance of at least 1 MPa, since the operating pressures in the fluidised bed reactor 14 reach values of from 0.1 MPa to 0.6 MPa. In addition, that first embodiment of the invention has a supply line 27 having a gas inlet aperture 10 through which a recycle gas and ethene are fed to the fluidised bed reactor 14. The recycle gas consists of unreacted ethene and unreacted oxygen, as well as of byproducts such as carbon monoxide, carbon dioxide and other residual gases conveyed in the cycle. By way of the recycle gas supply line 27 and the lower gas inlet 10 in the lower region of the fluidised bed reactor 14, the recycle gas is fed into the pressure vessel 28. The recycle gas flows via a gas distribution plate 29 into the fluidised bed 12 and establishes the catalyst particles 13 located in the fluidised bed, comprising copper(II) chloride-coated aluminium oxide particles, into a fluidised state, so that the oxychlorination reaction at the catalyst particles 13 can proceed in accordance with the following equation: C2H4 + 2HCI + 1/2O2 ↔ CI-CH2-CH2-CI + H2O. In that first embodiment of the apparatus 1 of the invention, the fluidised bed reactor 14 has a reaction height h which is subdivided into three gas inlet stages 19, 20 and 21, a hydrogen chloride-oxygen mixture being fed in via gas inlet 4 in stage 19 and reacting in an exothermic reaction with the ethene added to the recycle gas to form 1, 2-dichloroethane. In the lowest gas inlet stage, the heat of reaction is discharged by way of a first cooling circuit 16 in a cooling arrangement 15, and the reaction temperature is consequently kept stable at about 220°C to achieve optimum conversion of the ethene to the EDC product, and in such a manner that a minimum of by-products are formed through oxidation of the ethene. Arranged vertically thereabove is a second gas inlet stage 20 in which, via gas inlet 5, a further portion of hydrogen chloride and oxygen is in turn fed in and hence further ethene, which flows vertically through the fluidised bed reactor 14 with the recycle gas, is reacted to form the EDC product. Finally, the remaining residues of ethene are converted in an uppermost gas inlet stage 21 of the fluidised bed 12, hydrogen chloride and oxygen being added to the fluidised bed here, too, via gas inlet 6. For each of the three gas inlet stages a cooling circuit 16, 17 and 18 is provided, those cooling circuits being arranged vertically one above another in the fluidised bed reactor, there being cooling pipe bundles 30, 31 and 32 projecting into the fluidised bed. Before the reaction gases emerge from the fluidised bed reactor via the outlet 11, there is provided in the upper region of the fluidised bed reactor a fine-dust filter 33, which separates the minimal abraded catalyst material from the outflowing reaction gases, with the result that the purity of the 1, 2-dichloroethane obtained is improved. Figure 2 is a diagrammatic drawing of a fluidised bed reactor 14 of an apparatus 2 according to a second embodiment of the invention. Components having identical functions to those in Figure 1 are characterised by the same reference numerals and are not discussed further. The difference between the apparatus 2 of the second embodiment and that of the first embodiment shown in Figure 1 is that ethene is not only fed in with the recycle gas at the base of the pressure vessel 28 via the supply line 27 and the gas inlet 10, but additionally is added in the form of pure starting material via the gas inlet 7 in the second gas inlet stage 20 and via the gas inlet 8 in the third gas inlet stage 21 arranged vertically thereabove. The advantage of the apparatus 2 is that, as a result of the additional pure ethene feed in the second gas inlet stage 20 and in the third gas inlet stage 21, the process can be controlled more precisely towards minimum oxidation of the ethene to carbon monoxide and/or carbon dioxide. The gas inlets 4 to 8 are optimised in accordance with the specification DE 102 23 789 A 1, so that the material abraded from the catalyst particles 13 is minimised and the fine-dust filter 33 in the upper region of the pressure vessel is able to separate the abraded material from the reaction gases in the form of fine dust. Figure 3 is a diagrammatic drawing of a fluidised bed reactor 14 of an apparatus 3 according to a third embodiment of the invention. The third embodiment of the invention again has a cooling arrangement having three cooling circuits 16, 17 and 18 for discharging the waste heat from the exothermic oxychlorination process. The starting materials, however, are fed in in novel manner via the gas inlets 4 and 9. Thus, via the gas inlet 4 a mixture of hydrogen chloride and oxygen is fed into a distributor system 34 having vertical gas distributors 22, which consist of vertical pipes 23 arranged adjacent to one another. The inlet gas mixture is released from faces of the pipes 23 into the fluidised bed 12 in the fluidised bed reactor 14 transversely to the main stream of gas through the fluidised bed reactor 14. On the one hand, an almost continuous release of inlet gases into the fluidised bed 12 is achieved thereby, and on the other hand contact of catalyst particles 13 with the upper sides of the vertical pipes 23 is advantageously reduced by the crosscurrent, there especially being formed by the crosscurrent a film of gas which protects the surfaces of the pipes 23 and hence also the surfaces of the catalyst particles 13 against abrasion. For discharging the heat of reaction and for the thermal control of the oxychlorination in the fluidised bed reactor 14, there are again three cooling circuits 16, 17 and 18 arranged vertically one above another, which form a cooling arrangement 15. In similar manner, in addition to the ethene present in the recycle gas, pure ethene is fed via the inlet 9 to a vertical distributor system 35, which is constructed exactly like the distributor system 34. With the following Figure 4, a cutaway portion 36 of the distributor systems 34 and 35 arranged one in the other is shown on an enlarged scale. Figure 4 shows a cut-away portion 36, on an enlarged scale, of the vertical distributor systems 34 and 35 according to the apparatus 3 of the third embodiment of the invention. The vertical gas distributors 22 have a length I and stand upright in the fluidised bed region of the fluidised bed reactor 14 shown in Figure 3. In that embodiment of the invention, they consist of pipes having a casing of sintered metal, which has finely porous apertures and thus delivers the inlet gases continuously and in height-dependent manner to the fluidised bed chamber and reaction chamber of the fluidised bed reactor 14 of Figure 3. The arrow A indicates the main direction of the recycle gas, which flows vertically through the pressure vessel 28 of Figure 3, and the arrow directions Band b show the directions of the stream emerging from the faces 37 of the fine-pored distributors 26, which stream is orthogonal to the main stream direction A. Instead of the fine-pored vertical distributors 26, perforated distributors 25 from pipes 24 having perforations can be used, the faces 37 thereof having sieve-like apertures through which the conveyed gases emerge into the fluidised bed. The arrows C and c show the path and the outflow of ethene into the fluidised bed via the faces 37 of the vertical fine-pored distributors 26. The advantages of that manner of feeding-in the gases, especially with regard to minimising the oxidation of ethene to by-products such as carbon monoxide and carbon dioxide and with regard to minimising the material abraded from the catalyst particles 13, has already been discussed in detail and will not be repeated again here. The invention, insofar as it relates to the process of oxychlorination using the apparatus according to the invention, will now be explained in detail by way of the following Examples. Example 1 An oxychlorination reactor 14 having a two-stage fluidised bed 12 is used to prepare 1, 2-dichloroethane, the catalyst employed being Cu(II)Cl2. The plant is operated with an amount of recycle gas of 35 Nm3/h. 51 Nm3/h of ethene are added to the recycle gas stream, which has been preheated to 160°C The resulting gas mixture flows through the distributor plate 29 into the reactor. Via a gas inlet 4 of a first gas distributor 38 lying thereabove, a mixture of 13.5 Nm3/h of oxygen and 50 Nm3/h of hydrogen chloride are fed in over a first stage 19 to the fluidised bed of the fluidised bed reactor 14. The reaction of the starting materials to form 1, 2-dichloroethane and water takes place at 220°C and 0.35 MPa. The heat of reaction of the strongly exothermic reaction is discharged by way of a cooling pipe bundle 30 to a condensate. The reaction temperature in the reactor is regulated by partial vaporisation of the condensate in the cooling pipe bundle 30. Via a second gas distributor 39, lying between the first cooling pipe bundle 30 and a second cooling pipe bundle 31, 13.5 Nm3/h of oxygen and 50 Nm3/h of hydrogen chloride are fed via the gas inlet 5 into a second stage 20 of the fluidised bed reactor 14. In order to separate off entrained fragments of catalyst, the so-called abraded catalyst material, the reaction gas, after leaving the fluidised bed reactor 14, flows through, in a dry-operated cleaning zone 41 at a temperature of from 200 to 250°C (preferably 220°C) and a pressure of approximately from 0.1 MPa to 0.6 MPa (preferably 0.35 MPa), a very fine filter 33, in which virtually all of the catalyst is deposited. The reaction gas freed of abraded catalyst material and having a temperature of from 200 to 250°C, preferably approximately 220°C, is then conveyed via a line into a condenser, not shown, where the EDC and the water of reaction are condensed. In a gas separator, not shown, the condensed liquid is separated from the recycle gas. The EDC/ water mixture is conveyed via a pipeline to a separating vessel, not shown, in which the aqueous phase is separated from the EDC. The components that are not shown and their arrangement in an oxychlorination plant are known from the specification DE 40 33 048 A 1. The following starting material yields were ascertained by analyses of the byproducts, the waste gas and the waste water flow: Ethene: 97.8% Oxygen: 83.5% Hydrogen chloride: 99.0% Product quality: 1,1, 2-trichloroethane: 1924 ppm (w/w) Carbon tetrachloride: 2210 ppm (w/w) Chloroform: 1389 ppm (w/w) Catalyst output: 750 g EDC/kg catalyst and hour For comparison, the starting material yields of conventional oxychlorination with simple, that is, single-stage, starting material feed: Ethene: 95.8% Oxygen: 79.4% Hydrogen chloride: 98.6% Product quality: 1,1, 2-trichloroethane: 3343 ppm (w/w) Carbon tetrachloride: 2293 ppm (w/w) Chloroform: 1448 ppm (w/w) Catalyst output: 750 g EDC/kg catalyst and hour Example 2 An oxychlorination reactor 1 having a fluidised bed 12 is used to prepare 1,2- dichloroethane, the catalyst employed being CuCl2. The plant is operated with an amount of recycle gas of 35 Nm3/h. 28 Nm3/h of ethene are added to the recycle gas stream, which has been preheated to 160°C. The resulting gas mixture flows through the distributor plate 29 into the reactor. Via a gas distributor 4 lying thereabove, a mixture of 27 Nm3/h of oxygen and 100 Nm3/h of hydrogen chloride are fed to the fluidised bed. The reaction of the starting materials to form 1, 2-dichloroethane and water takes place at 220°C and 3.5 bar abs. The heat of reaction of the strongly exothermic reaction is discharged by way of a cooling pipe bundle 16 to a condensate. The reaction temperature in the reactor is regulated by partial vaporisation of the condensate in the cooling pipe bundle 30. Via a gas distributor 42, lying between the first cooling pipe bundle 30 and the second cooling pipe bundle 31, 23 Nm3/h of ethene are fed by the gas inlet 7 into the fluidised bed reactor 14. In order to separate off entrained fragments of catalyst, the so-called abraded catalyst material, the reaction gas, after leaving the fluidised bed reactor, flows through, in a dry-operated cleaning zone 41 at a temperature of from 200 to 250°C (preferably 220°C) and a pressure of approximately from 0.1 MPa to 0.6 MPa (preferably 0.35 MPa), a very fine filter 33, in which virtually all of the catalyst is deposited. The reaction gas freed of abraded catalyst material and having a temperature of from 200 to 250°C, preferably approximately 220°C, is then conveyed via a line into a condenser, not shown, where the EDC and the water of reaction are condensed. In a gas separator, not shown, the condensed liquid is separated from the recycle gas. The EDC/water mixture is conveyed via a pipeline to a separating vessel, not shown, in which the aqueous phase is separated from the EDC. The components that are not shown and their arrangement in an oxychlorination plant are known from the specification DE 40 33 048 A 1. The following starting material yields were ascertained by analyses of the byproducts, the waste gas and the waste water flow: Ethene: 98.1% Oxygen: 86.3% Hydrogen chloride: 99.2% Product quality: 1,1, 2-trichloroethane: 1790 ppm (w/w) Carbon tetrachloride: 2094 ppm (w/w) Chloroform: 1323 ppm (w/w) Catalyst output: 750 g EDC/kg catalyst and hour List of reference numerals 1 apparatus (1st embodiment) 2 apparatus (2nd embodiment) 3 apparatus (3rd embodiment) 4 gas inlet for hydrogen chloride and oxygen 5 gas inlet for hydrogen chloride and oxygen 6 gas inlet for hydrogen chloride and oxygen 7 gas inlet for ethene 8 gas inlet for ethene 9 gas inlet for ethene 10 lower gas inlet 11 reaction gas outlet 12 fluidised bed 13 catalyst particles 14 fluidised bed reactor 15 cooling arrangement 16 first cooling circuit or cooling pipe bundle 17 cooling circuit or cooling pipe bundle 18 cooling circuit or cooling pipe bundle 19 first gas inlet stage 20 second gas inlet stage 21 gas inlet stage 22 vertical gas distributor 23 vertical pipe 24 pipe (with perforations) 25 perforated distributor 26 fine-pored distributor 27 supply line 28 pressure-resistant vessel or pressure vessel 29 gas distribution plate 30 cooling pipe bundle 31 cooling pipe bundle 32 cooling pipe bundle 33 fine-dust filter 34 distributor system 35 distributor system 36 cut-away portion 37 casing face 38 gas distributor 39 gas distributor 40 gas distributor 41 cleaning zone 42 gas distributor 43 gas distributor 44 gas distributor h reaction height I length of the pipes WE CLAIM: 1. Apparatus for the oxychlorination of at least one alkene to at least one chlorinated alkane using hydrogen chloride and oxygen or an oxygen-containing gas, wherein the apparatus has gas inlets (4 to 10) into a fluidised bed (12) comprising catalyst particles (13) of a fluidised bed reactor (14) and at least one reaction gas outlet (11) above the fluidised bed (12), as well as a cooling arrangement (15) for the thermal control of an oxychlorination reaction, wherein a plurality of gas inlets (4 to 10) are arranged in vertical distribution along the fluidised bed (12) and the cooling arrangement (15) has cooling circuits (16,17,18) arranged vertically one above another which project into the fluidised bed. 2. Apparatus according to claim 1, wherein for feeding in hydrogen chloride and oxygen or an oxygen-containing gas, either individually or in the form of a mixture, there are provided at least two tiers (19, 20, 21) of gas inlets (4 to 10) arranged in vertical rungs. 3. Apparatus according to claim 1 or claim 2, wherein the gas inlets (4 to 10) for feeding in reaction gases extend over the reactor height (h), or over a portion of the reactor height, of the fluidised bed reactor (14) and have vertical gas distributors (22). 4. Apparatus according to claim 3, wherein the gas distributors (22) have vertically arranged pipes (23) which are arranged adjacent to one another in the fluidised bed (12) and have apertures distributed along their length (I) in the form of perforated distributors (25), which allow the reaction gases to flow in uniformly distributed manner over the reaction height (h) or over a portion of the reactor height into the fluidised bed (12) comprising catalyst particles (13). 5. Apparatus according to claim 3, wherein the gas distributors (22) have vertically arranged pipes (24) of open-pored material in the form of fine-pored distributors (26) which are arranged adjacent to one another in the fluidised bed (12), wherein the fine pores of the open-pored material allow the reaction gases to flow in uniformly distributed manner over the reactor height (h) or over a portion of the reactor height (h) into the fluidised bed (12) comprising catalyst particles (13). 6. Apparatus according to anyone of claims 1 to 5, wherein the gas inlets (4, 5, 6) for feeding in hydrogen chloride and oxygen or an oxygen-containing gas either individually or in the form of a mixture extend over the reactor height (h) or over a portion of the reactor height of the fluidised bed reactor (14) and have vertically arranged perforated distributors (25) or fine-pored distributors (26) preferably of sintered metal or sintered ceramics. 7. Apparatus according to anyone of claims 1 to 6, wherein at least one gas inlet (10) arranged in the lower region of the fluidised bed is provided for feeding in alkene gas together with a gas mixture conveyed in the cycle. 8. Apparatus according to anyone of claims 1 to 7, wherein a plurality of vertically tiered gas inlets (7, 8, 9) for feeding in alkene gas with or without a gas mixture conveyed in the cycle are provided in the region of the fluidised bed (12). 9. Apparatus according to anyone of claims 1 to 8, wherein the gas inlets (7, 8, 9, 10) for feeding in alkene gas with or without a gas mixture conveyed in the cycle extend over the reactor height (h) or over a portion of the reactor height of the fluidised bed reactor (14) and have vertically arranged perforated distributors (25) or fine-pored distributors (26) preferably of sintered metal or sintered ceramics. 10. Apparatus according to anyone of claims 1 to 9, wherein at least two cooling pipe bundles (16,17,18) arranged vertically one above another are provided as cooling arrangement (15) for discharging the heat of reaction. 11. Apparatus according to claim 10, wherein for discharging the heat of reaction a cooling pipe bundle (16, 17, 18) is arranged in such a manner that a cooling medium is arranged to be circulated in natural circulation. 12. Apparatus according to claim 10 or claim 11, wherein for discharging the heat of reaction at least one cooling pipe bundle (16, 17, 18) is connected to a circulating pump for a forced circulation of the cooling medium. 13. Process for the preparation of chlorinated alkanes by reaction of at least one alkene with a gas that contains hydrogen chloride and oxygen or an oxygen-containing gas in an oxychlorination reactor to form a reaction gas in a fluidised bed reactor (14), wherein the gas, which contains hydrogen chloride and oxygen or an oxygen-containing gas, is fed into the fluidised bed (12) in vertical distribution along the fluidised bed (12). 14. Process according to claim 13, wherein the feeding-in of hydrogen chloride and oxygen or oxygen-containing gas extends over the reactor height (h) or over a portion of the reactor height and is effected virtually continuously by fine distribution, preferably by means of perforated distributors (25) or by means of fine-pored distributors (26). 15. Process according to claim 13 or claim 14, wherein an alkene feed is effected together with a gas mixture conveyed in the cycle, in one stage or a plurality of stages. 16. Process according to claim 15, wherein the alkene feed is effected at one site (10) in a mixture with a gas mixture conveyed in the cycle and, in addition, is effected at at least one further site (7, 8) as pure starting material. 17. Process according to claim 15 or claim 16, wherein the alkene feed is effected as pure starting material at at least two sites (7, 8). 18. Process according to anyone of claims 15 to 17, wherein the alkene feed extends over the reactor height (h) or over a portion of the reactor height and is effected virtually continuously by fine distribution, preferably by means of perforated distributors (25) or fine-pored distributors (26). 19. Process according to anyone of claims 15 to 18, wherein the alkene feed is effected at one site (10) in a mixture with the gas mixture conveyed in the cycle and, in addition, extends over the reactor height (h) or over a portion of the reactor height and is effected virtually continuously by fine distribution, preferably by means of perforated distributors (25) or fine-pored distributors (26). 20. Process according to anyone of claims 13 to 19, wherein the heat of reaction is discharged into at least 2 or more cooling pipe bundles (16, 17, 18) arranged one above another. 21. Process according to claim 20, wherein discharge of the heat of reaction by way of the cooling medium, is operated in natural circulation. 22. Process according to claim 20 or 21, wherein discharge of the heat of reaction by way of the cooling medium, is operated in forced circulation. ABSTRACT The invention relates to an apparatus (1) and to a process for the oxychlorination of alkenes to chlorinated alkanes using hydrogen chloride and oxygen. The apparatus (1) has gas inlets (4, 5, 6) into a fluidised bed (12) comprising catalyst particles (13) of a fluidised bed reactor (14) and at least one reaction gas outlet (11) above the fluidised bed (12) as well as a cooling arrangement (15) for the thermal control of an exothermic oxychlorination reaction. A plurality of gas inlets (4, 5, 6) for the same inlet gases are arranged in vertical distribution along the fluidised bed (12). The cooling arrangement (15) has cooling circuits (16,17, 18) arranged vertically one above another which project into the fluidised bed (12). Using the apparatus (1), dichloroethane is prepared on a large industrial scale with optimum use of the starting material ethene.

Full Text

FORM 2
THE PATENT ACT 1970 (39 of 1970)
&
The Patents Rules, 2003 COMPLETE SPECIFICATION
(See Section 10, and rule 13
TITLE OF INVENTION
APPARATUS AND PROCESS FOR OXYCHLORINATION

APPLICANT(S)
a) Name : VINNOLIT GMBH & CO. KG
b) Nationality : GERMAN Company
c) Address : PROFIT-CENTER VINTEC
WERK GENDORF
84 504 BURGKIRCHEN
GERMANY

PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed : -

The invention relates to an apparatus and to a process for the oxychlorination of alkenes to chlorinated alkanes using hydrogen chloride and oxygen. For that purpose the apparatus has gas inlets into a fluidised bed comprising catalyst particles of a fluidised bed reactor. In addition, the fluidised bed reactor has at least one reaction gas outlet above the fluidised bed as well as a cooling arrangement for the thermal control of an exothermic oxychlorination reaction.
Such an apparatus and a process for the preparation of 1, 2-dichJoroethane is known from the specification DE 40 33 048 A 1. In the known process, an alkene, such as ethene, is reacted by single-stage oxychlorination to form 1,2-dichloroethane, also referred to as "EDC", using hydrogen chloride and oxygen or an oxygen-containing gas such as air, at temperatures of from 200 to 250°C and pressures of from 2 to 6 bar (0.2 MPa to 0.6 MPa), in the presence of a catalyst consisting of copper(II) chloride on carrier particles, in accordance with the following equation:
C2H4, + 2HCI + 1/2O2 ↔ CI-CH2-CH2-CI + H2O.
The catalyst particles are held in a fluidised bed, as the reaction zone, which is fluidised by a recycle gas, the input gases being introduced into the fluidised bed under pressure via gas inlets. Via a gas outlet above the fluidised bed, the reaction gases, the water and l,2dichloroethane and also unreacted ethene, unreacted oxygen and by-products, such as carbon monoxide, carbon dioxide and residual gases, are discharged and for the most part conveyed in the cycle after liquid 1 ,2-dichloroethane and water have been removed in condensation stages. The gas conveyed in the cycle, composed of by-products and unreacted input gases, is mixed with ethene and conveyed to the reaction zone, that is, the fluidised bed in the lower region of the fluidised bed reactor.
The oxygen and the hydrogen chloride gas stream are mixed prior to the reaction zone and are added in an amount that leads to the reaction of the hydrogen chloride in the reaction zone and to the inevitably resulting formation of a small amount of

carbon monoxide and carbon dioxide from the ethene fed in. The content of oxygen in the recycle gas is kept so small that a flammable gas mixture is not formed in the cycle. The single-stage process known from the specification DE 40 33 048 A 1 and the apparatus associated therewith have the disadvantage that, if the amount of catalyst is increased in order to increase the productivity of the fluidised bed reactor and in addition increase the EDC production per catalyst amount and time, then there is an over-proportional increase in the oxidation rate of ethene and hence also an over-proportional increase in the by-products such as carbon monoxide and carbon dioxide.
Consequently, although a single-stage arrangement is compact and favourable in terms of investment costs, it has the disadvantage of higher ethene losses resulting from oxidation to carbon dioxide and carbon monoxide. Thus, the ethene and oxygen yields, especially, are worsened relative to investment costs as a result of the increase in reactor productivity when there is a simultaneous increase in the capacity of existing single-stage arrangements. Consequent disadvantages are accordingly increased by-product formation and increased operating costs.
A further aspect of the invention concerns an improvement in the introduction of gas into the fluidised bed reactor. In that connection, there is known for introducing gas into a fluidised bed reactor, from the specification DE 102 23 789 A 1, a device that has gas inlet pipes which have gas fluidising means upstream from and/or at their discharge orifices. Those means are alleged to bring about a greater fluidisation of the catalyst particles composed of aluminium oxide carriers having a copper(II) chloride coating and to minimise abraded material.
In customary fluidised bed plants used on a large industrial scale, abraded material originates as a result of the catalyst particles in the upper region of the oxychlorination reactor being deposited and recovered in a plurality of series-connected cyclones, with the result that the majority of the particles are retained in the reactor. But catalyst dust originates from abraded catalyst both in the cyclones

and on the walls of the reactor vessel as well as on the gas inlet pipes, so that the abraded catalyst passes into the reaction gas leaving the reactor and reaches the working up of the 1,2-dichloroethane where it has to be separated off again.
The aim of the present invention is therefore to provide an apparatus and a process for the oxychlorination of alkenes to chlorinated alkanes using hydrogen chloride and oxygen. Using the apparatus and the process, preferably 1, 2-dichloroethane is to be prepared on a large industrial scale with the use of commercial oxychlorination catalysts and a high specific catalyst output, wherein the oxidation of ethene to byproducts, such as carbon dioxide, is to be minimised, the starting material yields are to be maximised and EDC is to be yielded with improved purity, especially with an unchanged low level, or reduced level, of abraded catalyst.
The aim is achieved by the subject of the independent claims. Advantageous further developments of the invention are disclosed in the dependent claims.
According to the invention, an apparatus is provided for the oxychlorination of at least one alkene to at least one chlorinated alkane using hydrogen chloride and oxygen or an oxygencontaining gas, wherein the apparatus has gas inlets into a fluidised bed comprising catalyst particles of a fluidised bed reactor. In addition, the apparatus has at least one reaction gas outlet above the fluidised bed as well as a cooling arrangement for the thermal control of an oxychlorination reaction. In that new apparatus, a plurality of gas inlets are arranged in vertical distribution along the fluidised bed. The cooling arrangement furthermore has cooling circuits arranged vertically one above another which project into the fluidised bed.
An advantage of this apparatus is that, as a result of the vertically distributed gas inlets for inlet gases and starting materials, an optimum amount of catalyst with optimum control of the exothermic oxychlorination reaction can be provided, especially since the cooling circuits are also arranged in vertical tiers, one above another, in the fluidised bed. Consequently, the optimum reaction temperature

provided hitherto for single-stage processes can be retained and nevertheless the total amount of catalyst located in the reactor, and also the amount of inlet gases, can be increased as desired. This is governed solely by the height of the fluidised bed reactor. Consequently, the advantage of this apparatus over a single-stage oxychlorination apparatus is that optimum conditions for the conversion of ethene can be achieved by feeding hydrogen chloride and oxygen into the vertically divided regions of the fluidised bed with its catalyst regions in tiers one above another.
In addition, in a preferred embodiment of the apparatus according to the invention, for feeding in hydrogen chloride and oxygen or oxygen-containing gases, either individually or in the form of a mixture, there are provided at least two tiers of gas inlets arranged in vertical rungs. In those tiered gas inlets it is also possible for optimum shaping of the gas inlet orifices, such as are known from the above-mentioned specification DE 102 23 789 A 1, to be used.
That has the advantage that the resulting 1, 2-dichloroethane is charged with a minimum content of catalyst dust. In the apparatus according to the invention the content of catalyst dust can be minimised even further by having a fine-dust filter connected upstream of the reactor gas outlet of the fluidised bed reactor, which filter separates the reaction gases emerging from the reactor and the catalyst dust from one another. In that way, a higher degree of purity of the EDC starting product is advantageously also achieved.
In a further preferred embodiment of the apparatus according to the invention, newly designed gas inlets are provided for feeding in inlet gases and feeding in starting materials, which inlets extend over the reactor height, or at least over a portion of the reactor height, of the fluidised bed reactor and have vertical gas distributors. The vertical gas distributors have the outer form of pipes, from the faces of which the inlet gases discharge directly into the fluidised bed region transversely to the main stream. While the circulating stream, which keeps the catalyst particles in fluid motion, flows vertically through the fluidised bed reactor from a bottom side

to a top side of the fluidised bed reactor as the main stream of gas, the inlet gases are introduced continuously transversely to the main stream into the fluidised bed along the height of the fluidised bed reactor through the vertical gas distributors. Since the flow vectors of the inlet gases relative to the recycle gas are perpendicular to one another, an optimum introduction of fluidising gas which is extremely gentle for the catalyst particles is achieved.
In addition, the vertical gas distributors can have apertures distributed along their length in the form of so-called perforated distributors, it being possible for the cross-section of the apertures to be kept extremely small to strengthen the fluidising action.
On the other hand, instead of perforated distributors it is also possible to use rod-shaped gas distributors in the form of vertically arranged pipes formed with open-pored material, the pipes being arranged adjacent to one another in the fluidised bed. As a result of the fine pores of the open-pored material, the reaction gases are able to flow in a uniformly distributed manner, transversely to the main stream of gas, over the height of the reactor or over a portion of the height of the reactor into the fluidised bed comprising catalyst particles. Using such open-pored pipes, for example sintered ceramic pipes, the inlet gas stream is further refined, so that the catalyst particles are gently blended with the inlet gas in the fluidised bed region. In addition, the faces of the vertical pipes are coated with a gas film by the emerging gases, so that mechanical contact with the catalyst particles is reduced, resulting in reduced abrasion of catalyst material in the fluidised bed.
Preferably, arrangement is made for the apparatus according to the invention to be provided with gas inlets for feeding in hydrogen chloride and oxygen or oxygen-containing gases either individually or in the form of a mixture over the reactor height or over a portion of the reactor height of the fluidised bed reactor, the hydrogen chloride and/ or the oxygen or the oxygen-containing gases emerging from the vertically arranged perforated distributors or from the fine-pored

distributors, which have preferably been produced from sintered metal or sintered ceramics. Unlike the single-stage introduction of inlet gases such as hydrocarbon gas, oxygen and hydrogen chloride known from the prior art, inlet gas is thus, as a result of the vertical distributors, uniformly blended over an extended region of the reactor with an ethene flowing vertically in the main stream.
In addition, in a preferred embodiment of the apparatus, an alkene gas feed together with a gas mixture conveyed in the cycle has at least one gas inlet arranged in the lower region of the fluidised bed. That lower gas inlet with recycle gas conveyed in the cycle provides for a main gas stream of ethene and recycle gas from a lower inlet in the lower region of the fluidised bed reactor to an upper outlet in the upper region of the fluidised bed reactor, fine dust being captured to a very large extent by a fine-dust filter arranged in the upper region of the fluidised bed reactor.
hi a further preferred embodiment of the apparatus according to the invention, in addition to the lower gas inlet for a gas mixture of ethene and recycle gas, a vertically tiered gas inlet is provided in the region of the fluidised bed. In that embodiment of the apparatus, a portion of the required ethene can be fed into the fluidised bed reactor in the lower region together with the recycle gas, and a further portion of pure ethene can be fed in in a first stage or a plurality of subsequent stages. In that arrangement, a plurality of vertically tiered gas inlets for feeding in alkene gas are arranged vertically one above another.
In a further preferred embodiment of the apparatus according to the invention, arrangement is also made for gas inlets to be provided for feeding in solely alkene gas by way of vertical distributors along the reactor height or at least a portion of the reactor height of the fluidised bed reactor. In that arrangement, perforated distributors or fine-pored distributors, preferably of sintered metal or sintered ceramics, are arranged in the apparatus for the alkene gas feed. As a result of that new construction for the introduction of gas via perforated distributors and/or

vertical fine-pored distributors, losses of catalyst can also advantageously be further reduced for the multi-stage process according to the invention.
For discharging the heat of reaction and hence for the thermal control of the oxychlorination process, there are provided as a cooling arrangement in the novel apparatus at least two cooling pipe bundles arranged vertically one above another. As a result of those cooling pipe bundles arranged vertically one above another, it is possible at any stage of the gas inlet feed for an optimum equilibrium to be achieved between ethene reactions with hydrogen chloride and oxygen, so that the combustion of the ethene by oxygen to by-products such as carbon monoxide and carbon dioxide is kept extremely low. That reduction in oxidation rates for ethene to by-products is surprising, because the reaction temperatures used hitherto in single-stage processes can be retained unchanged, despite increased loading with amounts of catalyst and despite increased loading of the new apparatus with inlet gases and reaction gases.
Discharge of the heat of reaction from the cooling pipe bundles can be effected by natural circulation when the cooling pipe bundles are appropriately arranged to allow natural circulation of the cooling medium by the effects of gravity. On the other hand, provision can also be made for the apparatus to be equipped with circulating pumps for the cooling pipe bundles to achieve forced circulation of the cooling medium.
A further aspect of the invention concerns a process for the preparation of at least one chlorinated alkane by reaction of at least one alkene with hydrogen chloride and oxygen or an oxygen-containing gas in an oxychlorination reactor to form a reaction gas in a fluidised bed reactor. For that purpose, the hydrogen chloride and oxygen or the oxygen-containing gas are fed into the fluidised bed in vertical distribution along the fluidised bed. As a result of the vertical distribution of the inlet gases hydrogen chloride and oxygen-containing gas or oxygen, the single stage feed, which leads to

increased combustion of the ethene to byproducts such as carbon monoxide and carbon dioxide, is avoided.
In addition, in a preferred arrangement of the process, the feeding-in of hydrogen chloride and oxygen or oxygen-containing gas can extend over the height of the reactor or over a portion of the height of the reactor and can be effected virtually continuously by fine distribution, preferably by means of perforated distributors or by means of fine-pored distributors. The advantages of the vertically arranged fine-pored distributors having a gas outflow orthogonal to the main direction of the ethene-containing recycle gas have already been discussed hereinabove and will therefore not be explained again here.
In addition to that almost continuous feed, the feeding-in of ethene as the alkene together with a gas mixture conveyed in the cycle can be effected in one stage or a plurality of stages. When it is carried out in one stage, the ethene is fed in in the lower region of the fluidised bed furnace. In the case of multi-stage feed, gas inlets for introducing ethene are additionally provided in the middle and upper regions of the fluidised bed.
Preference is thus given to a process in which the feeding-in of alkene is effected at one site in a mixture with a gas mixture conveyed in the cycle and, in addition, is effected at at least one further site as pure starting material. On the other hand it is also possible for the alkene to be fed in at one site in a mixture with the gas mixture conveyed in the cycle and for an additional feed-in to be effected virtually continuously over the height of the reactor or over a portion of the height of the reactor by a fine distribution preferably being effected by means of perforated distributors or fine-pored distributors. Such a process not only has the advantage of making optimum use of the ethene to produce 1, 2-dichloroethane but also has the advantage of an appreciable reduction in the abrasion of catalyst to catalyst dust, since the gases flowing out of the vertically arranged distributors transversely to the direction of the main stream form a gas film which protects the catalyst particles

against contact with the pipe-shaped vertical distributors and the surfaces thereof. That protective gas film is especially impervious in the case of fine-pored distributors, since the gas stream flows almost continuously.
The process is additionally optimised by discharge of the heat of reaction into at least two or more cooling pipe bundles arranged one above another. The heat of reaction can therefore be optimally related to the oxychlorination procedure in the respective stages of the fluidised bed reactor. To that end, discharge of the heat of reaction can be conducted by way of the cooling medium in natural circulation, or can be effected by forced circulation by using a circulating pump.
The invention will now be explained in detail in relation to the apparatus, with reference to the accompanying Figures.
Figure 1 is a diagrammatic drawing of a fluidised bed reactor of an apparatus
according to a first embodiment of the invention;
Figure 2 is a diagrammatic drawing of a fluidised bed reactor of an apparatus
according to a second embodiment of the invention;
Figure 3 is a diagrammatic drawing of a fluidised bed reactor of an apparatus
according to a third embodiment of the invention;
Figure 4 shows a cut-away portion, on an enlarged scale, of the vertical distributor
systems according to the apparatus of the third embodiment of the
invention shown in Figure 3.
Figure 1 is a diagrammatic drawing of a fluidised bed reactor 14 of an apparatus 1 according to a first embodiment of the invention. The fluidised bed reactor 14 has a pressure-resistant vessel 28 having a pressure resistance of at least 1 MPa, since the operating pressures in the fluidised bed reactor 14 reach values of from 0.1 MPa to 0.6 MPa. In addition, that first embodiment of the invention has a supply line 27 having a gas inlet aperture 10 through which a recycle gas and ethene are fed to the fluidised bed reactor 14.

The recycle gas consists of unreacted ethene and unreacted oxygen, as well as of byproducts such as carbon monoxide, carbon dioxide and other residual gases conveyed in the cycle. By way of the recycle gas supply line 27 and the lower gas inlet 10 in the lower region of the fluidised bed reactor 14, the recycle gas is fed into the pressure vessel 28. The recycle gas flows via a gas distribution plate 29 into the fluidised bed 12 and establishes the catalyst particles 13 located in the fluidised bed, comprising copper(II) chloride-coated aluminium oxide particles, into a fluidised state, so that the oxychlorination reaction at the catalyst particles 13 can proceed in accordance with the following equation:
C2H4 + 2HCI + 1/2O2 ↔ CI-CH2-CH2-CI + H2O.
In that first embodiment of the apparatus 1 of the invention, the fluidised bed reactor 14 has a reaction height h which is subdivided into three gas inlet stages 19, 20 and 21, a hydrogen chloride-oxygen mixture being fed in via gas inlet 4 in stage 19 and reacting in an exothermic reaction with the ethene added to the recycle gas to form 1, 2-dichloroethane. In the lowest gas inlet stage, the heat of reaction is discharged by way of a first cooling circuit 16 in a cooling arrangement 15, and the reaction temperature is consequently kept stable at about 220°C to achieve optimum conversion of the ethene to the EDC product, and in such a manner that a minimum of by-products are formed through oxidation of the ethene.
Arranged vertically thereabove is a second gas inlet stage 20 in which, via gas inlet 5, a further portion of hydrogen chloride and oxygen is in turn fed in and hence further ethene, which flows vertically through the fluidised bed reactor 14 with the recycle gas, is reacted to form the EDC product. Finally, the remaining residues of ethene are converted in an uppermost gas inlet stage 21 of the fluidised bed 12, hydrogen chloride and oxygen being added to the fluidised bed here, too, via gas inlet 6. For each of the three gas inlet stages a cooling circuit 16, 17 and 18 is provided, those cooling circuits being arranged vertically one above another in the fluidised bed reactor, there being cooling pipe bundles 30, 31 and 32 projecting into the fluidised

bed. Before the reaction gases emerge from the fluidised bed reactor via the outlet 11, there is provided in the upper region of the fluidised bed reactor a fine-dust filter 33, which separates the minimal abraded catalyst material from the outflowing reaction gases, with the result that the purity of the 1, 2-dichloroethane obtained is improved.
Figure 2 is a diagrammatic drawing of a fluidised bed reactor 14 of an apparatus 2 according to a second embodiment of the invention. Components having identical functions to those in Figure 1 are characterised by the same reference numerals and are not discussed further. The difference between the apparatus 2 of the second embodiment and that of the first embodiment shown in Figure 1 is that ethene is not only fed in with the recycle gas at the base of the pressure vessel 28 via the supply line 27 and the gas inlet 10, but additionally is added in the form of pure starting material via the gas inlet 7 in the second gas inlet stage 20 and via the gas inlet 8 in the third gas inlet stage 21 arranged vertically thereabove.
The advantage of the apparatus 2 is that, as a result of the additional pure ethene feed in the second gas inlet stage 20 and in the third gas inlet stage 21, the process can be controlled more precisely towards minimum oxidation of the ethene to carbon monoxide and/or carbon dioxide. The gas inlets 4 to 8 are optimised in accordance with the specification DE 102 23 789 A 1, so that the material abraded from the catalyst particles 13 is minimised and the fine-dust filter 33 in the upper region of the pressure vessel is able to separate the abraded material from the reaction gases in the form of fine dust.
Figure 3 is a diagrammatic drawing of a fluidised bed reactor 14 of an apparatus 3 according to a third embodiment of the invention. The third embodiment of the invention again has a cooling arrangement having three cooling circuits 16, 17 and 18 for discharging the waste heat from the exothermic oxychlorination process. The starting materials, however, are fed in in novel manner via the gas inlets 4 and 9. Thus, via the gas inlet 4 a mixture of hydrogen chloride and oxygen is fed into a distributor system 34 having vertical gas distributors 22, which consist of vertical

pipes 23 arranged adjacent to one another. The inlet gas mixture is released from faces of the pipes 23 into the fluidised bed 12 in the fluidised bed reactor 14 transversely to the main stream of gas through the fluidised bed reactor 14.
On the one hand, an almost continuous release of inlet gases into the fluidised bed 12 is achieved thereby, and on the other hand contact of catalyst particles 13 with the upper sides of the vertical pipes 23 is advantageously reduced by the crosscurrent, there especially being formed by the crosscurrent a film of gas which protects the surfaces of the pipes 23 and hence also the surfaces of the catalyst particles 13 against abrasion. For discharging the heat of reaction and for the thermal control of the oxychlorination in the fluidised bed reactor 14, there are again three cooling circuits 16, 17 and 18 arranged vertically one above another, which form a cooling arrangement 15. In similar manner, in addition to the ethene present in the recycle gas, pure ethene is fed via the inlet 9 to a vertical distributor system 35, which is constructed exactly like the distributor system 34. With the following Figure 4, a cutaway portion 36 of the distributor systems 34 and 35 arranged one in the other is shown on an enlarged scale.
Figure 4 shows a cut-away portion 36, on an enlarged scale, of the vertical distributor systems 34 and 35 according to the apparatus 3 of the third embodiment of the invention. The vertical gas distributors 22 have a length I and stand upright in the fluidised bed region of the fluidised bed reactor 14 shown in Figure 3. In that embodiment of the invention, they consist of pipes having a casing of sintered metal, which has finely porous apertures and thus delivers the inlet gases continuously and in height-dependent manner to the fluidised bed chamber and reaction chamber of the fluidised bed reactor 14 of Figure 3. The arrow A indicates the main direction of the recycle gas, which flows vertically through the pressure vessel 28 of Figure 3, and the arrow directions Band b show the directions of the stream emerging from the faces 37 of the fine-pored distributors 26, which stream is orthogonal to the main stream direction A.

Instead of the fine-pored vertical distributors 26, perforated distributors 25 from pipes 24 having perforations can be used, the faces 37 thereof having sieve-like apertures through which the conveyed gases emerge into the fluidised bed. The arrows C and c show the path and the outflow of ethene into the fluidised bed via the faces 37 of the vertical fine-pored distributors 26. The advantages of that manner of feeding-in the gases, especially with regard to minimising the oxidation of ethene to by-products such as carbon monoxide and carbon dioxide and with regard to minimising the material abraded from the catalyst particles 13, has already been discussed in detail and will not be repeated again here.
The invention, insofar as it relates to the process of oxychlorination using the apparatus according to the invention, will now be explained in detail by way of the following Examples.
Example 1
An oxychlorination reactor 14 having a two-stage fluidised bed 12 is used to prepare
1, 2-dichloroethane, the catalyst employed being Cu(II)Cl2.
The plant is operated with an amount of recycle gas of 35 Nm3/h. 51 Nm3/h of ethene are added to the recycle gas stream, which has been preheated to 160°C The resulting gas mixture flows through the distributor plate 29 into the reactor. Via a gas inlet 4 of a first gas distributor 38 lying thereabove, a mixture of 13.5 Nm3/h of oxygen and 50 Nm3/h of hydrogen chloride are fed in over a first stage 19 to the fluidised bed of the fluidised bed reactor 14. The reaction of the starting materials to form 1, 2-dichloroethane and water takes place at 220°C and 0.35 MPa. The heat of reaction of the strongly exothermic reaction is discharged by way of a cooling pipe bundle 30 to a condensate. The reaction temperature in the reactor is regulated by partial vaporisation of the condensate in the cooling pipe bundle 30.
Via a second gas distributor 39, lying between the first cooling pipe bundle 30 and a second cooling pipe bundle 31, 13.5 Nm3/h of oxygen and 50 Nm3/h of hydrogen

chloride are fed via the gas inlet 5 into a second stage 20 of the fluidised bed reactor 14. In order to separate off entrained fragments of catalyst, the so-called abraded catalyst material, the reaction gas, after leaving the fluidised bed reactor 14, flows through, in a dry-operated cleaning zone 41 at a temperature of from 200 to 250°C (preferably 220°C) and a pressure of approximately from 0.1 MPa to 0.6 MPa (preferably 0.35 MPa), a very fine filter 33, in which virtually all of the catalyst is deposited.
The reaction gas freed of abraded catalyst material and having a temperature of from 200 to 250°C, preferably approximately 220°C, is then conveyed via a line into a condenser, not shown, where the EDC and the water of reaction are condensed. In a gas separator, not shown, the condensed liquid is separated from the recycle gas. The EDC/ water mixture is conveyed via a pipeline to a separating vessel, not shown, in which the aqueous phase is separated from the EDC. The components that are not shown and their arrangement in an oxychlorination plant are known from the specification DE 40 33 048 A 1.
The following starting material yields were ascertained by analyses of the byproducts, the waste gas and the waste water flow:
Ethene: 97.8%
Oxygen: 83.5%
Hydrogen chloride: 99.0%
Product quality:
1,1, 2-trichloroethane: 1924 ppm (w/w)
Carbon tetrachloride: 2210 ppm (w/w)
Chloroform: 1389 ppm (w/w)
Catalyst output: 750 g EDC/kg catalyst and hour
For comparison, the starting material yields of conventional oxychlorination with simple, that is, single-stage, starting material feed:

Ethene: 95.8%
Oxygen: 79.4%
Hydrogen chloride: 98.6%
Product quality:
1,1, 2-trichloroethane: 3343 ppm (w/w)
Carbon tetrachloride: 2293 ppm (w/w)
Chloroform: 1448 ppm (w/w)
Catalyst output: 750 g EDC/kg catalyst and hour
Example 2
An oxychlorination reactor 1 having a fluidised bed 12 is used to prepare 1,2-
dichloroethane, the catalyst employed being CuCl2.
The plant is operated with an amount of recycle gas of 35 Nm3/h. 28 Nm3/h of ethene are added to the recycle gas stream, which has been preheated to 160°C. The resulting gas mixture flows through the distributor plate 29 into the reactor. Via a gas distributor 4 lying thereabove, a mixture of 27 Nm3/h of oxygen and 100 Nm3/h of hydrogen chloride are fed to the fluidised bed. The reaction of the starting materials to form 1, 2-dichloroethane and water takes place at 220°C and 3.5 bar abs. The heat of reaction of the strongly exothermic reaction is discharged by way of a cooling pipe bundle 16 to a condensate. The reaction temperature in the reactor is regulated by partial vaporisation of the condensate in the cooling pipe bundle 30.
Via a gas distributor 42, lying between the first cooling pipe bundle 30 and the second cooling pipe bundle 31, 23 Nm3/h of ethene are fed by the gas inlet 7 into the fluidised bed reactor 14. In order to separate off entrained fragments of catalyst, the so-called abraded catalyst material, the reaction gas, after leaving the fluidised bed reactor, flows through, in a dry-operated cleaning zone 41 at a temperature of from 200 to 250°C (preferably 220°C) and a pressure of approximately from 0.1 MPa to 0.6 MPa (preferably 0.35 MPa), a very fine filter 33, in which virtually all of the catalyst is deposited.

The reaction gas freed of abraded catalyst material and having a temperature of from 200 to 250°C, preferably approximately 220°C, is then conveyed via a line into a condenser, not shown, where the EDC and the water of reaction are condensed. In a gas separator, not shown, the condensed liquid is separated from the recycle gas. The EDC/water mixture is conveyed via a pipeline to a separating vessel, not shown, in which the aqueous phase is separated from the EDC. The components that are not shown and their arrangement in an oxychlorination plant are known from the specification DE 40 33 048 A 1.
The following starting material yields were ascertained by analyses of the byproducts, the waste gas and the waste water flow:
Ethene: 98.1%
Oxygen: 86.3%
Hydrogen chloride: 99.2%
Product quality:
1,1, 2-trichloroethane: 1790 ppm (w/w)
Carbon tetrachloride: 2094 ppm (w/w)
Chloroform: 1323 ppm (w/w)
Catalyst output: 750 g EDC/kg catalyst and hour

List of reference numerals

1 apparatus (1st embodiment)
2 apparatus (2nd embodiment)
3 apparatus (3rd embodiment)
4 gas inlet for hydrogen chloride and oxygen
5 gas inlet for hydrogen chloride and oxygen
6 gas inlet for hydrogen chloride and oxygen
7 gas inlet for ethene
8 gas inlet for ethene
9 gas inlet for ethene
10 lower gas inlet
11 reaction gas outlet
12 fluidised bed
13 catalyst particles
14 fluidised bed reactor
15 cooling arrangement
16 first cooling circuit or cooling pipe bundle
17 cooling circuit or cooling pipe bundle
18 cooling circuit or cooling pipe bundle
19 first gas inlet stage
20 second gas inlet stage
21 gas inlet stage
22 vertical gas distributor
23 vertical pipe
24 pipe (with perforations)
25 perforated distributor
26 fine-pored distributor
27 supply line
28 pressure-resistant vessel or pressure vessel
29 gas distribution plate
30 cooling pipe bundle

31 cooling pipe bundle
32 cooling pipe bundle
33 fine-dust filter
34 distributor system
35 distributor system
36 cut-away portion
37 casing face
38 gas distributor
39 gas distributor
40 gas distributor
41 cleaning zone
42 gas distributor
43 gas distributor
44 gas distributor
h reaction height
I length of the pipes

WE CLAIM:
1. Apparatus for the oxychlorination of at least one alkene to at least one chlorinated alkane using hydrogen chloride and oxygen or an oxygen-containing gas, wherein the apparatus has gas inlets (4 to 10) into a fluidised bed (12) comprising catalyst particles (13) of a fluidised bed reactor (14) and at least one reaction gas outlet (11) above the fluidised bed (12), as well as a cooling arrangement (15) for the thermal control of an oxychlorination reaction, wherein a plurality of gas inlets (4 to 10) are arranged in vertical distribution along the fluidised bed (12) and the cooling arrangement (15) has cooling circuits (16,17,18) arranged vertically one above another which project into the fluidised bed.
2. Apparatus according to claim 1, wherein for feeding in hydrogen chloride and oxygen or an oxygen-containing gas, either individually or in the form of a mixture, there are provided at least two tiers (19, 20, 21) of gas inlets (4 to 10) arranged in vertical rungs.
3. Apparatus according to claim 1 or claim 2, wherein the gas inlets (4 to 10) for feeding in reaction gases extend over the reactor height (h), or over a portion of the reactor height, of the fluidised bed reactor (14) and have vertical gas distributors (22).
4. Apparatus according to claim 3, wherein the gas distributors (22) have vertically arranged pipes (23) which are arranged adjacent to one another in the fluidised bed (12) and have apertures distributed along their length (I) in the form of perforated distributors (25), which allow the reaction gases to flow in uniformly distributed manner over the reaction height (h) or over a portion of the reactor height into the fluidised bed (12) comprising catalyst particles (13).
5. Apparatus according to claim 3, wherein the gas distributors (22) have vertically arranged pipes (24) of open-pored material in the form of fine-pored distributors (26) which are arranged adjacent to one another in the fluidised

bed (12), wherein the fine pores of the open-pored material allow the reaction gases to flow in uniformly distributed manner over the reactor height (h) or over a portion of the reactor height (h) into the fluidised bed (12) comprising catalyst particles (13).
6. Apparatus according to anyone of claims 1 to 5, wherein the gas inlets (4, 5, 6) for feeding in hydrogen chloride and oxygen or an oxygen-containing gas either individually or in the form of a mixture extend over the reactor height (h) or over a portion of the reactor height of the fluidised bed reactor (14) and have vertically arranged perforated distributors (25) or fine-pored distributors (26) preferably of sintered metal or sintered ceramics.
7. Apparatus according to anyone of claims 1 to 6, wherein at least one gas inlet (10) arranged in the lower region of the fluidised bed is provided for feeding in alkene gas together with a gas mixture conveyed in the cycle.
8. Apparatus according to anyone of claims 1 to 7, wherein a plurality of vertically tiered gas inlets (7, 8, 9) for feeding in alkene gas with or without a gas mixture conveyed in the cycle are provided in the region of the fluidised bed (12).
9. Apparatus according to anyone of claims 1 to 8, wherein the gas inlets (7, 8, 9, 10) for feeding in alkene gas with or without a gas mixture conveyed in the cycle extend over the reactor height (h) or over a portion of the reactor height of the fluidised bed reactor (14) and have vertically arranged perforated distributors (25) or fine-pored distributors (26) preferably of sintered metal or sintered ceramics.
10. Apparatus according to anyone of claims 1 to 9, wherein at least two cooling pipe bundles (16,17,18) arranged vertically one above another are provided as cooling arrangement (15) for discharging the heat of reaction.

11. Apparatus according to claim 10, wherein for discharging the heat of reaction a cooling pipe bundle (16, 17, 18) is arranged in such a manner that a cooling medium is arranged to be circulated in natural circulation.
12. Apparatus according to claim 10 or claim 11, wherein for discharging the heat of reaction at least one cooling pipe bundle (16, 17, 18) is connected to a circulating pump for a forced circulation of the cooling medium.
13. Process for the preparation of chlorinated alkanes by reaction of at least one alkene with a gas that contains hydrogen chloride and oxygen or an oxygen-containing gas in an oxychlorination reactor to form a reaction gas in a fluidised bed reactor (14), wherein the gas, which contains hydrogen chloride and oxygen or an oxygen-containing gas, is fed into the fluidised bed (12) in vertical distribution along the fluidised bed (12).
14. Process according to claim 13, wherein the feeding-in of hydrogen chloride and oxygen or oxygen-containing gas extends over the reactor height (h) or over a portion of the reactor height and is effected virtually continuously by fine distribution, preferably by means of perforated distributors (25) or by means of fine-pored distributors (26).
15. Process according to claim 13 or claim 14, wherein an alkene feed is effected together with a gas mixture conveyed in the cycle, in one stage or a plurality of stages.
16. Process according to claim 15, wherein the alkene feed is effected at one site (10) in a mixture with a gas mixture conveyed in the cycle and, in addition, is effected at at least one further site (7, 8) as pure starting material.
17. Process according to claim 15 or claim 16, wherein the alkene feed is effected as pure starting material at at least two sites (7, 8).
18. Process according to anyone of claims 15 to 17, wherein the alkene feed extends over the reactor height (h) or over a portion of the reactor height and is

effected virtually continuously by fine distribution, preferably by means of perforated distributors (25) or fine-pored distributors (26).
19. Process according to anyone of claims 15 to 18, wherein the alkene feed is effected at one site (10) in a mixture with the gas mixture conveyed in the cycle and, in addition, extends over the reactor height (h) or over a portion of the reactor height and is effected virtually continuously by fine distribution, preferably by means of perforated distributors (25) or fine-pored distributors (26).
20. Process according to anyone of claims 13 to 19, wherein the heat of reaction is discharged into at least 2 or more cooling pipe bundles (16, 17, 18) arranged one above another.
21. Process according to claim 20, wherein discharge of the heat of reaction by way of the cooling medium, is operated in natural circulation.
22. Process according to claim 20 or 21, wherein discharge of the heat of reaction by way of the cooling medium, is operated in forced circulation.

ABSTRACT
The invention relates to an apparatus (1) and to a process for the oxychlorination of alkenes to chlorinated alkanes using hydrogen chloride and oxygen. The apparatus (1) has gas inlets (4, 5, 6) into a fluidised bed (12) comprising catalyst particles (13) of a fluidised bed reactor (14) and at least one reaction gas outlet (11) above the fluidised bed (12) as well as a cooling arrangement (15) for the thermal control of an exothermic oxychlorination reaction. A plurality of gas inlets (4, 5, 6) for the same inlet gases are arranged in vertical distribution along the fluidised bed (12). The cooling arrangement (15) has cooling circuits (16,17, 18) arranged vertically one above another which project into the fluidised bed (12). Using the apparatus (1), dichloroethane is prepared on a large industrial scale with optimum use of the starting material ethene.

Documents:

1955-mum-2007-abstract.doc

1955-mum-2007-abstract.pdf

1955-mum-2007-claims.doc

1955-mum-2007-claims.pdf

1955-MUM-2007-CORRESPONDENCE(19-7-2010).pdf

1955-MUM-2007-CORRESPONDENCE(6-4-2010).pdf

1955-mum-2007-correspondence-others.pdf

1955-mum-2007-correspondence-received.pdf

1955-mum-2007-description (complete).pdf

1955-mum-2007-drawings.pdf

1955-MUM-2007-FORM 3(19-7-2010).pdf

1955-mum-2007-form-1.pdf

1955-mum-2007-form-18.pdf

1955-mum-2007-form-2.doc

1955-mum-2007-form-2.pdf

1955-mum-2007-form-3.pdf

1955-mum-2007-form-5.pdf

1955-MUM-2007-GENERAL POWER OF ATTORNEY(19-7-2010).pdf

1955-MUM-2007-PETITION UNDER RULE 137(19-7-2010).pdf

1955-MUM-2007-REPLY TO EXAMINATION REPORT(19-7-2010).pdf

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Patent Number

264094

Indian Patent Application Number

1955/MUM/2007

PG Journal Number

50/2014

Publication Date

12-Dec-2014

Grant Date

05-Dec-2014

Date of Filing

03-Oct-2007

Name of Patentee

VINNOLIT GMBH & CO.

Applicant Address

PROFIT-CENTER VINTEC WERK GENDORF 84504 BURGKIRCHEN

Inventors:

#	Inventor's Name	Inventor's Address
1	PETER KAMMERHOFER	ORTLEHNER STR. 48 84508 BURGKIRCHEN
2	KLAUS KREJCI	MARKTLER STR.40 84489 BURGHAUSEN

PCT International Classification Number

B01J21/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	102006049546.2	2006-10-20	Germany