CA2297428C - Process for the preparation of 1,2-dichloroethane from oxychlorination - Google Patents
Process for the preparation of 1,2-dichloroethane from oxychlorination Download PDFInfo
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- CA2297428C CA2297428C CA002297428A CA2297428A CA2297428C CA 2297428 C CA2297428 C CA 2297428C CA 002297428 A CA002297428 A CA 002297428A CA 2297428 A CA2297428 A CA 2297428A CA 2297428 C CA2297428 C CA 2297428C
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- oxygen
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- 238000000034 method Methods 0.000 title claims abstract description 24
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 238000000465 moulding Methods 0.000 claims abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007858 starting material Substances 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005977 Ethylene Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 230000000717 retained effect Effects 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000000376 reactant Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000788 chromium alloy Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 238000011005 laboratory method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
- B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/006—Separating solid material from the gas/liquid stream by filtration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1872—Details of the fluidised bed reactor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process for the preparation of 1,2-dichloroethane by reacting ethene with hydrogen chloride and oxygen or an oxygen-containing gas over a copper-containing catalyst in a fluidized bed, which comprises introducing at least one of the starting material streams - hydrogen chloride and oxygen - directly into the fluidized bed, via feed lines made from a porous gas-permeable molding, and introducing the ethylene and the recycled gas stream over a base prepared from porous gas-permeable material or provided with a molding made from porous gas-permeable material.
Description
Process For The Preparation Of 1,2-Dichloraethane From Oxychlorination Background of the Invention 1) Field of the Invention The invention relates to a process for the preparation of 1,2-dichloroethane by an oxychlorination procedure and to an apparatus for carrying it out.
2) Background Art Oxychlorination generally means the reaction of an alkene with hydrogen chloride and oxygen or an oxygen-containing gas, such as air, to form a saturated chlorinated alkane. The reaction takes place in accordance with the following equation, which, by way of example, shows the reaction of ethene to give 1,2-dichloroethane, called "EDC"
below, CZH4 + 2HC1 = '-~ OZ G~ C1-CHZ-CHZ-C1 + HzO.
In one version of this process which is frequently utilized on an industrial scale, the catalyst used is a fluidized bed, the catalyst consisting essentially of copper chloride on an aluminum oxide support. The ethene and the oxygen or the oxygen-containing gas are, separately from one another, introduced into this catalyst bed, the hydrogen chloride usually being metered in together with the oxygen or the oxygen-containing gas. It is ensured that the reactants firstly make contact with the fluidized bed before they encountered one another for the reaction. This avoids the formation of explosive mixtures.
Australian Patent No. 702305 discloses an apparatus and its use for oxychlorination, which apparatus comprises a reactor having a delimited fluidized catalyst bed, in which, within this fluidized catalyst bed, a first gas feed line (distributing pipes) which contains nozzles distributed over the entire cross section of the reactor, is fixed. The nozzles feed into pipes which lead the exiting gas stream essentially in countercurrent to the gas stream which fluidizes the catalyst. The space between the lower ends of these pipes and the upper ends of the pipes which are incorporated in the boundary between the fluidized catalyst bed and that of the rest of the reactor with the second gas feed line, forms a mixing zone which is dimensioned such that, on the one hand, mixing of the reactants with the catalyst can take place here and that, on the other hand, there is no longer any great mutual erosive stressing of the pipes and of the lower boundary.
3j Description of the Pref~rr~d Embodiments Preferred embodiments of this apparatus have pipes which pass through the boundary to the fluidized catalyst bed, where nozzles are arranged below the boundary but above the lower ends of the pipes. Furthermore, these nozzles are notable for the fact that they are fixed at such a distance from the upper ends of the pipes that the upwardly directed rate of flow of the gas jets from the nozzles to the upper ends of the pipes is evened out over the particular cross section of a pipe. Here, the nozzles are fixed to the lower ends of the pipes at a distance of one diameter of a pipe, and the length of the pipe is chosen such that the downwardly directed rate of flow of the gas jets from the nozzles to the lower ends of the pipes is evened out over the particular cross section of a pipe. The nozzles have varying diameters, so that the quantity of gas conveyed via the gas feed pipe is uniformly distributed over the cross section of the reactor.
A process with similar apparatus is known from PCT
publication WO 9419099.
All of the known processes and the apparatuses associated therewith are complex in structure and permit only a very uncontrolled introduction of the starting material gas streams into the reactor.
The object was therefore to provide a process in which the starting materials can be fed into the reactor in as simple and also as finely dispersed a manner as possible.
The invention provides a process for the preparation of 1,2-dichloroethane by reacting ethene with hydrogen chloride and oxygen or an oxygen-containing gas over a copper containing catalyst in a fluidized bed, which comprises introducing at least one of the starting material streams - hydrogen chloride and oxygen - directly into the fluidized bed, via feed lines made from a porous gas-. permeable molding, and introducing the ethene and the recycled gas stream over a base prepared from porous gas permeable material or provided with a molding made from a porous gas-permeable material.
According to the invention, the reactants, ethene on the one hand and oxygen on the other hand, the term also being intended to include an oxygen-containing gas, are thus introduced such that at least one of these reactants is fed into the fluidized bed over a porous molding, in finely divided form. The hydrogen chloride can be metered into or mixed with one or both of said reactants in a manner known per se.
Preferably, the oxygen on the one hand and the ethene on the other hand are both fed into the fluidized catalyst bed in a finely divided form such that in each case, as described above, the hydrogen chloride can be fed into the fluidized bed with one or both of the reactants.
The feed lines are preferably constructed in the form of pipes, similar to a filter candle or a number of tubular elements made from porous materials arranged, for example, in parallel. Suitable examples are frits made from glass or ceramic, as are also known from laboratory techniques. Thin porous elements made from sintered metals which have the corresponding necessary chemical and thermal resistance are preferably suitable. Suitable for this _ purpose are the materials used in the construction of chemical apparatuses, such as stainless steel alloys or very corrosion-resistant alloys, as are commercially available under the names ~INCONEL (trade mark of Inco Ltd.;
nickel/chromium alloy), ~MONEL (trade mark of Inco Ltd.;
nickel/copper alloy), ~HASTELLOY (nickel alloy).
If a countercurrent of the reactants is envisaged, the introduction of the gas with the porous molding within the fluidized bed is designed such that the gas discharges in countercurrent to the gas stream through the lower boundary of the fluidized bed. If this countercurrent is not desired, the introduction of gas can be directed in other flow directions or can take place in all directions.
The pores of the porous filter elements in the gassing apparatus expediently have a diameter of from 0.5 to 50 Vim, preferably from 5 to 20 N.m.
Another aspect of the invention relates to the lower boundary of the fluidized bed which, according to the invention, is formed as a porous molding. Suitable for this purpose are, for example, frits made from glass or ceramic, as are also known from laboratory techniques. Thin porous elements made from sintered metals which have the corresponding necessary chemical and thermal resistance are preferably suitable. Suitable for this purpose are the materials used in the construction of chemical apparatuses, - such as stainless steel alloys or very corrosion-resistant alloys, as are commercially available under the names ~INCONEL (trade mark of Inco Ltd.; nickel/chromium alloy), ~MONEL (trade mark of Inco Ltd.; nickel/copper alloy), ~HASTELLOY (nickel alloy).
The invention further provides an apparatus for carrying out the process, comprising a reactor (2) equipped with a fluidized bed, which reactor is fitted with lines (1) and (3) for introducing the starting material streams, and with at least one line (5) for drawing off the products, wherein the lines for introducing the starting materials have been prepared from porous material.
Preference is given to an embodiment of the apparatus wherein, prior to drawing off the products via a line (5), said products are filtered with a filter device (4) made from porous material.
Preference is also given to an embodiment of the apparatus wherein, for the introduction of the ethylene and of the recycled gas stream, the reactor (2) is equipped with a base (12) prepared from a porous gas-permeable material or provided with a molding made from porous gas-permeable material.
below, CZH4 + 2HC1 = '-~ OZ G~ C1-CHZ-CHZ-C1 + HzO.
In one version of this process which is frequently utilized on an industrial scale, the catalyst used is a fluidized bed, the catalyst consisting essentially of copper chloride on an aluminum oxide support. The ethene and the oxygen or the oxygen-containing gas are, separately from one another, introduced into this catalyst bed, the hydrogen chloride usually being metered in together with the oxygen or the oxygen-containing gas. It is ensured that the reactants firstly make contact with the fluidized bed before they encountered one another for the reaction. This avoids the formation of explosive mixtures.
Australian Patent No. 702305 discloses an apparatus and its use for oxychlorination, which apparatus comprises a reactor having a delimited fluidized catalyst bed, in which, within this fluidized catalyst bed, a first gas feed line (distributing pipes) which contains nozzles distributed over the entire cross section of the reactor, is fixed. The nozzles feed into pipes which lead the exiting gas stream essentially in countercurrent to the gas stream which fluidizes the catalyst. The space between the lower ends of these pipes and the upper ends of the pipes which are incorporated in the boundary between the fluidized catalyst bed and that of the rest of the reactor with the second gas feed line, forms a mixing zone which is dimensioned such that, on the one hand, mixing of the reactants with the catalyst can take place here and that, on the other hand, there is no longer any great mutual erosive stressing of the pipes and of the lower boundary.
3j Description of the Pref~rr~d Embodiments Preferred embodiments of this apparatus have pipes which pass through the boundary to the fluidized catalyst bed, where nozzles are arranged below the boundary but above the lower ends of the pipes. Furthermore, these nozzles are notable for the fact that they are fixed at such a distance from the upper ends of the pipes that the upwardly directed rate of flow of the gas jets from the nozzles to the upper ends of the pipes is evened out over the particular cross section of a pipe. Here, the nozzles are fixed to the lower ends of the pipes at a distance of one diameter of a pipe, and the length of the pipe is chosen such that the downwardly directed rate of flow of the gas jets from the nozzles to the lower ends of the pipes is evened out over the particular cross section of a pipe. The nozzles have varying diameters, so that the quantity of gas conveyed via the gas feed pipe is uniformly distributed over the cross section of the reactor.
A process with similar apparatus is known from PCT
publication WO 9419099.
All of the known processes and the apparatuses associated therewith are complex in structure and permit only a very uncontrolled introduction of the starting material gas streams into the reactor.
The object was therefore to provide a process in which the starting materials can be fed into the reactor in as simple and also as finely dispersed a manner as possible.
The invention provides a process for the preparation of 1,2-dichloroethane by reacting ethene with hydrogen chloride and oxygen or an oxygen-containing gas over a copper containing catalyst in a fluidized bed, which comprises introducing at least one of the starting material streams - hydrogen chloride and oxygen - directly into the fluidized bed, via feed lines made from a porous gas-. permeable molding, and introducing the ethene and the recycled gas stream over a base prepared from porous gas permeable material or provided with a molding made from a porous gas-permeable material.
According to the invention, the reactants, ethene on the one hand and oxygen on the other hand, the term also being intended to include an oxygen-containing gas, are thus introduced such that at least one of these reactants is fed into the fluidized bed over a porous molding, in finely divided form. The hydrogen chloride can be metered into or mixed with one or both of said reactants in a manner known per se.
Preferably, the oxygen on the one hand and the ethene on the other hand are both fed into the fluidized catalyst bed in a finely divided form such that in each case, as described above, the hydrogen chloride can be fed into the fluidized bed with one or both of the reactants.
The feed lines are preferably constructed in the form of pipes, similar to a filter candle or a number of tubular elements made from porous materials arranged, for example, in parallel. Suitable examples are frits made from glass or ceramic, as are also known from laboratory techniques. Thin porous elements made from sintered metals which have the corresponding necessary chemical and thermal resistance are preferably suitable. Suitable for this _ purpose are the materials used in the construction of chemical apparatuses, such as stainless steel alloys or very corrosion-resistant alloys, as are commercially available under the names ~INCONEL (trade mark of Inco Ltd.;
nickel/chromium alloy), ~MONEL (trade mark of Inco Ltd.;
nickel/copper alloy), ~HASTELLOY (nickel alloy).
If a countercurrent of the reactants is envisaged, the introduction of the gas with the porous molding within the fluidized bed is designed such that the gas discharges in countercurrent to the gas stream through the lower boundary of the fluidized bed. If this countercurrent is not desired, the introduction of gas can be directed in other flow directions or can take place in all directions.
The pores of the porous filter elements in the gassing apparatus expediently have a diameter of from 0.5 to 50 Vim, preferably from 5 to 20 N.m.
Another aspect of the invention relates to the lower boundary of the fluidized bed which, according to the invention, is formed as a porous molding. Suitable for this purpose are, for example, frits made from glass or ceramic, as are also known from laboratory techniques. Thin porous elements made from sintered metals which have the corresponding necessary chemical and thermal resistance are preferably suitable. Suitable for this purpose are the materials used in the construction of chemical apparatuses, - such as stainless steel alloys or very corrosion-resistant alloys, as are commercially available under the names ~INCONEL (trade mark of Inco Ltd.; nickel/chromium alloy), ~MONEL (trade mark of Inco Ltd.; nickel/copper alloy), ~HASTELLOY (nickel alloy).
The invention further provides an apparatus for carrying out the process, comprising a reactor (2) equipped with a fluidized bed, which reactor is fitted with lines (1) and (3) for introducing the starting material streams, and with at least one line (5) for drawing off the products, wherein the lines for introducing the starting materials have been prepared from porous material.
Preference is given to an embodiment of the apparatus wherein, prior to drawing off the products via a line (5), said products are filtered with a filter device (4) made from porous material.
Preference is also given to an embodiment of the apparatus wherein, for the introduction of the ethylene and of the recycled gas stream, the reactor (2) is equipped with a base (12) prepared from a porous gas-permeable material or provided with a molding made from porous gas-permeable material.
The invention has a number of advantages:
The elements made from porous material cause the gases introduced into the fluidized catalyst layer to be introduced as very fine bubbles. These are naturally able to make contact with the catalyst surface much more easily and therefore react much more quickly with the reactant. As a result, the reaction becomes decisively more controllable and thus more selective, i.e., the formation of by-products is suppressed and the yield increases. Additionally, by introducing fine gas bubbles, the danger of the reaction being uncontrollable is significantly reduced, which signifies a further increase in the safety of the reaction.
In the same way, the homogeneous gas distribution resulting therefrom also acts over the entire reactor cross section, which likewise improves mass transfer. The very fine gas bubbles also permit the distance between the cooling elements in the fluidized bed to be significantly reduced, meaning that a considerably greater area of cooling surface is available per volume unit in the reaction zone. This increased cooling capacity for its part effects a reaction which can be better controlled, but can lead to the reactor volume being significantly reduced.
Another significant advantage is that in the process according to the invention it is not possible for a finely divided catalyst to penetrate through the gas inlet devices made from porous material, should the introduction of reaction gases be interrupted. This dispenses with the hitherto required storage of a flushing gas such as nitrogen, the volume of which has unnecessarily burdened the utilization of waste gas.
A particularly compact construction of the oxychlorination reactor is made possible by the catalyst being largely retained within the reactor ,by fine filtration, coarse and fine fractions of the catalyst preferably being retained in one step. This filtration by means of a porous gas-permeable molding can, for example, take place by way of filter candles, bag filters or cartridge filters. Fine filtration retains particles > 1 ~.m.
This makes it possible to dispense with the hitherto required cyclones for retention of the catalyst.
As a result of the reaction gases flowing uniformly, the friction in the catalyst is also considerably reduced.
As a result, the particle size spectrum in the catalyst remains essentially constant over long periods, which in turn contributes to an evening out of the reaction. Apart from the advantages already given with regard to improved selectivity a.nd safety, further advantages are that the service lives of the plant are considerably extended, and expensive downtimes and maintenance times are reduced.
The elements made from porous material cause the gases introduced into the fluidized catalyst layer to be introduced as very fine bubbles. These are naturally able to make contact with the catalyst surface much more easily and therefore react much more quickly with the reactant. As a result, the reaction becomes decisively more controllable and thus more selective, i.e., the formation of by-products is suppressed and the yield increases. Additionally, by introducing fine gas bubbles, the danger of the reaction being uncontrollable is significantly reduced, which signifies a further increase in the safety of the reaction.
In the same way, the homogeneous gas distribution resulting therefrom also acts over the entire reactor cross section, which likewise improves mass transfer. The very fine gas bubbles also permit the distance between the cooling elements in the fluidized bed to be significantly reduced, meaning that a considerably greater area of cooling surface is available per volume unit in the reaction zone. This increased cooling capacity for its part effects a reaction which can be better controlled, but can lead to the reactor volume being significantly reduced.
Another significant advantage is that in the process according to the invention it is not possible for a finely divided catalyst to penetrate through the gas inlet devices made from porous material, should the introduction of reaction gases be interrupted. This dispenses with the hitherto required storage of a flushing gas such as nitrogen, the volume of which has unnecessarily burdened the utilization of waste gas.
A particularly compact construction of the oxychlorination reactor is made possible by the catalyst being largely retained within the reactor ,by fine filtration, coarse and fine fractions of the catalyst preferably being retained in one step. This filtration by means of a porous gas-permeable molding can, for example, take place by way of filter candles, bag filters or cartridge filters. Fine filtration retains particles > 1 ~.m.
This makes it possible to dispense with the hitherto required cyclones for retention of the catalyst.
As a result of the reaction gases flowing uniformly, the friction in the catalyst is also considerably reduced.
As a result, the particle size spectrum in the catalyst remains essentially constant over long periods, which in turn contributes to an evening out of the reaction. Apart from the advantages already given with regard to improved selectivity a.nd safety, further advantages are that the service lives of the plant are considerably extended, and expensive downtimes and maintenance times are reduced.
In other respects, the oxychlorination process is carried out in a manner known per se;
The temperatures in the reaction zone of the reactor are between 200°C and 270°C, preferably between 215°C and 230°C, particularly preferably between 220°C and 225°C. The pressure established in the process is from 2.5 x 105 to 5 x 105 Pa, preferably from 3 x 10' to 4 x 105 Pa, particularly preferably from 3.4 x 10' to 3.5 to 10' Pa (in each case pressure above atmospheric pressure).
Here, per mole of ethane, from 1.5 to 2.5 mol, preferably from 1.8 to 2.1 mol, of hydrogen chloride are used, and from 0.2 to 0.9 mol, preferably from 0.4 to 0.7 mol of oxygen, it being ensured, in a manner know per se, that the ethene or the oxygen first makes contact with the catalyst before it meets the other reactants, as is taught, for example, in Australian Patent No. 702305.
Alternatives to this can also involve operating in other known ways such that explosive gas mixtures are avoided.
The reaction gas is also worked up in a customary manner. In this regard, reference may be made, for example, to the publications cited at the beginning.
The temperatures in the reaction zone of the reactor are between 200°C and 270°C, preferably between 215°C and 230°C, particularly preferably between 220°C and 225°C. The pressure established in the process is from 2.5 x 105 to 5 x 105 Pa, preferably from 3 x 10' to 4 x 105 Pa, particularly preferably from 3.4 x 10' to 3.5 to 10' Pa (in each case pressure above atmospheric pressure).
Here, per mole of ethane, from 1.5 to 2.5 mol, preferably from 1.8 to 2.1 mol, of hydrogen chloride are used, and from 0.2 to 0.9 mol, preferably from 0.4 to 0.7 mol of oxygen, it being ensured, in a manner know per se, that the ethene or the oxygen first makes contact with the catalyst before it meets the other reactants, as is taught, for example, in Australian Patent No. 702305.
Alternatives to this can also involve operating in other known ways such that explosive gas mixtures are avoided.
The reaction gas is also worked up in a customary manner. In this regard, reference may be made, for example, to the publications cited at the beginning.
The example below serves to illustrate the invention in more detail. The figures given in brackets refer to Figure 1.
_ Example 1:
5910 Nm3/h of hydrogen chloride at a temperature of 150°C and 1600 Nm3/h of oxygen at a temperature of I10°C
were introduced together into the reactor (2), directly into the lower section of the fluidized bed, via the line (1) and over horizontally arranged porous tubular metal elements (11). 3000 Nm3/h of ethylene were heated together with the recycled gas to 150°C and fed into the reactor (2) via the line (3). The introduction of this ethene-enriched recycled gas stream took place via a base which had been equipped with a molding made from porous sintered metal (12). The reactor (2) contained 40 t of fluidized bed catalyst (aluminum oxide with a copper content of 4~ by weight) having the following particle distribution:
Particle size [~.~m] Fraction (passage) [ o by weight) _ -< 20 4 < 32 6 < 41 26 < 50 54 < 61 82 < 82 96 The heat of the reaction was dissipated via a hot-water circuit with the recovery of steam. After it had left the fluidized bed, the reaction gas, for deposition of entrained catalyst particles in the upper part of the reactor, flowed through the finest filter (4), where virtually all of the catalyst was deposited. The reaction gas freed from the catalyst and having a temperature of 220°C was passed via the line (5) into the quenching column (6), where the processing water was condensed and fed via line (7) to the waste-water processing. The copper content in the quenching water was < 0.05 mg/1. The top stream, consisting essentially of EDC and recycled gas, was fed via IO line (8) to the EDC processing.
The finest filter (4) was cleaned in a differential pressure-controlled manner via line (9) using nitrogen which was heated to 180°C in the preheater (10). The retention rate was > 99.99%. After operation for three months, it was not possible to establish any significant change in the particle size distribution in the fluidized bed.
_ Example 1:
5910 Nm3/h of hydrogen chloride at a temperature of 150°C and 1600 Nm3/h of oxygen at a temperature of I10°C
were introduced together into the reactor (2), directly into the lower section of the fluidized bed, via the line (1) and over horizontally arranged porous tubular metal elements (11). 3000 Nm3/h of ethylene were heated together with the recycled gas to 150°C and fed into the reactor (2) via the line (3). The introduction of this ethene-enriched recycled gas stream took place via a base which had been equipped with a molding made from porous sintered metal (12). The reactor (2) contained 40 t of fluidized bed catalyst (aluminum oxide with a copper content of 4~ by weight) having the following particle distribution:
Particle size [~.~m] Fraction (passage) [ o by weight) _ -< 20 4 < 32 6 < 41 26 < 50 54 < 61 82 < 82 96 The heat of the reaction was dissipated via a hot-water circuit with the recovery of steam. After it had left the fluidized bed, the reaction gas, for deposition of entrained catalyst particles in the upper part of the reactor, flowed through the finest filter (4), where virtually all of the catalyst was deposited. The reaction gas freed from the catalyst and having a temperature of 220°C was passed via the line (5) into the quenching column (6), where the processing water was condensed and fed via line (7) to the waste-water processing. The copper content in the quenching water was < 0.05 mg/1. The top stream, consisting essentially of EDC and recycled gas, was fed via IO line (8) to the EDC processing.
The finest filter (4) was cleaned in a differential pressure-controlled manner via line (9) using nitrogen which was heated to 180°C in the preheater (10). The retention rate was > 99.99%. After operation for three months, it was not possible to establish any significant change in the particle size distribution in the fluidized bed.
Claims (12)
1. A process for the preparation of 1,2-dichloroethane in a reactor by reacting ethene with hydrogen chloride and oxygen or an oxygen-containing gas over a copper-containing catalyst in a fluidized bed, which comprises introducing at least one of the starting material streams - hydrogen chloride and oxygen - directly into the fluidized bed, via feed lines made from a porous gas-permeable molding, and introducing the ethylene and a recycled gas stream over a base prepared from porous gas-permeable material or provided with a molding made from porous gas-permeable material.
2. The process as claimed in claim 1, wherein the porous moldings consist of glass or ceramic.
3. The process as claimed in claim 1, wherein the porous moldings consist of sintered metals.
4. The process as claimed in claim 1, wherein the porous moldings have pores with a diameter of from 0.5 to 50 µm.
5. The process as claimed in claim 1, wherein, in the reactor, the gas can be introduced in all directions through the porous moldings.
6. The process as claimed in claim 1, wherein the catalyst which has been entrained from the fluidized bed is largely retained within the reactor by fine filters made from a porous gas-permeable molding.
7. The process as claimed in claim 1, wherein particles >
1 µm are retained as a result of a fine filtration process.
1 µm are retained as a result of a fine filtration process.
8. The process as claimed in claim 7, wherein the fine filtration process is carried out using filter candles, bag filters or cartridge filters.
9. The process as claimed in claim 8, wherein the filter candles are made from sintered metal or from ceramic.
10. An apparatus for carrying out the process of any one of claims 1 to 9, comprising a reactor equipped with a fluidized bed, which reactor is fitted with two lines for introducing the starting material streams, and with at least one line for drawing off the products, wherein the two lines for introducing the starting materials and situated within the reactor have been prepared from porous material.
11. The apparatus as claimed in claim 10, wherein the apparatus is provided with a filter device fitted to the line for drawing off the products.
12. The apparatus as claimed in claim 10, wherein, for the introduction of the ethylene and of the recycled gas stream, the reactor is equipped with a base prepared from porous gas-permeable material or provided with a molding made from porous gas-permeable material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19903335A DE19903335A1 (en) | 1999-01-28 | 1999-01-28 | Process for the preparation of 1,2-dichloroethane from oxychlorination |
| DE19903335.8 | 1999-01-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2297428A1 CA2297428A1 (en) | 2000-07-28 |
| CA2297428C true CA2297428C (en) | 2003-12-30 |
Family
ID=7895641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002297428A Expired - Fee Related CA2297428C (en) | 1999-01-28 | 2000-01-28 | Process for the preparation of 1,2-dichloroethane from oxychlorination |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1023939B1 (en) |
| CN (1) | CN1136172C (en) |
| CA (1) | CA2297428C (en) |
| DE (2) | DE19903335A1 (en) |
| NO (1) | NO20000432L (en) |
| PL (1) | PL338098A1 (en) |
| RU (1) | RU2176993C2 (en) |
| TR (1) | TR200000253A2 (en) |
| ZA (1) | ZA200000312B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10107089A1 (en) * | 2001-02-13 | 2002-08-29 | Vinnolit Technologie Gmbh & Co | direct condensation |
| DE10238811B4 (en) * | 2002-08-23 | 2006-04-13 | Austria Wirtschaftsservice Gesellschaft mit beschränkter Haftung | Oxychlorination of olefins and aromatics using a novel fluidized bed reactor concept |
| US7718811B2 (en) | 2002-11-26 | 2010-05-18 | Ineos Europe Limited | Oxidation process in fluidised bed reactor |
| FR2881732B1 (en) * | 2005-02-08 | 2007-11-02 | Solvay | PROCESS FOR THE PURIFICATION OF HYDROGEN CHLORIDE |
| TW200732038A (en) * | 2006-01-13 | 2007-09-01 | Bp Chem Int Ltd | Process and apparatus for reducing the probability of ignition in fluid bed-catalysed oxidation reactions |
| CN108786669B (en) | 2017-04-27 | 2021-01-12 | 中国科学院大连化学物理研究所 | Fluidized bed gas distributor, reactor using same and method for co-producing p-xylene and low-carbon olefin |
| CN108794294B (en) * | 2017-04-27 | 2020-12-11 | 中国科学院大连化学物理研究所 | Fluidized bed gas distributor, reactor using the same, and method for producing para-xylene and co-producing light olefins |
| CN107188780A (en) * | 2017-05-22 | 2017-09-22 | 太仓阳鸿石化有限公司 | The storage method and storage arrangement of dichloroethanes |
| CN111659322A (en) * | 2019-03-06 | 2020-09-15 | 浙江佳汇新材料有限公司 | Device and process for preparing 1,1,1, 3-tetrachloropropane |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3679373A (en) * | 1968-12-16 | 1972-07-25 | Ppg Industries Inc | Reactor for use with fluidized beds |
| GB1272037A (en) * | 1969-11-14 | 1972-04-26 | Sir Soc Italiana Resine Spa | Process for the manufacture of dichloroethane |
| DE3106983A1 (en) * | 1981-02-25 | 1982-09-09 | Hoechst Ag, 6000 Frankfurt | "METHOD FOR PRODUCING 1,2-DICHLORETHANE" |
| JPS59158904A (en) * | 1983-03-01 | 1984-09-08 | Kawasaki Heavy Ind Ltd | Fluidized-bed type combustion furnace |
| DE4004886A1 (en) * | 1989-04-11 | 1990-10-18 | Foerder & Anlagentechnik Gmbh | Fluidised bed furnace structure - has floor formed from porous ceramic bricks encased in metal housing |
| DE4305001A1 (en) * | 1993-02-18 | 1994-08-25 | Hoechst Ag | Oxychlorination device |
| DE19505664C2 (en) * | 1995-02-20 | 1996-12-12 | Hoechst Ag | Device and its use for oxychlorination |
| DE19753165B4 (en) * | 1997-12-01 | 2006-10-19 | Vinnolit Monomer Gmbh & Co. Kg | Process for the preparation of 1,2-dichloroethane by oxychlorination |
-
1999
- 1999-01-28 DE DE19903335A patent/DE19903335A1/en not_active Withdrawn
-
2000
- 2000-01-13 DE DE50000141T patent/DE50000141D1/en not_active Expired - Lifetime
- 2000-01-13 EP EP00100199A patent/EP1023939B1/en not_active Expired - Lifetime
- 2000-01-25 ZA ZA200000312A patent/ZA200000312B/en unknown
- 2000-01-27 RU RU2000101775/04A patent/RU2176993C2/en not_active IP Right Cessation
- 2000-01-27 TR TR2000/00253A patent/TR200000253A2/en unknown
- 2000-01-27 PL PL00338098A patent/PL338098A1/en not_active Application Discontinuation
- 2000-01-27 CN CNB001004670A patent/CN1136172C/en not_active Expired - Fee Related
- 2000-01-27 NO NO20000432A patent/NO20000432L/en unknown
- 2000-01-28 CA CA002297428A patent/CA2297428C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| RU2176993C2 (en) | 2001-12-20 |
| PL338098A1 (en) | 2000-07-31 |
| TR200000253A2 (en) | 2000-09-21 |
| NO20000432D0 (en) | 2000-01-27 |
| CA2297428A1 (en) | 2000-07-28 |
| EP1023939A1 (en) | 2000-08-02 |
| EP1023939B1 (en) | 2002-04-17 |
| NO20000432L (en) | 2000-07-31 |
| ZA200000312B (en) | 2000-09-27 |
| DE50000141D1 (en) | 2002-05-23 |
| CN1265389A (en) | 2000-09-06 |
| CN1136172C (en) | 2004-01-28 |
| DE19903335A1 (en) | 2000-08-17 |
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