CA1207802A - Process for the manufacture of 1,2-dichloroethane - Google Patents
Process for the manufacture of 1,2-dichloroethaneInfo
- Publication number
- CA1207802A CA1207802A CA000396999A CA396999A CA1207802A CA 1207802 A CA1207802 A CA 1207802A CA 000396999 A CA000396999 A CA 000396999A CA 396999 A CA396999 A CA 396999A CA 1207802 A CA1207802 A CA 1207802A
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- reaction
- reaction space
- ethylene
- space
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
Abstract of the disclosure:
A process is described for the manufacture of 1,2-dichloroethane by the direct chlorination and oxy-chlorination of ethylene in a common reaction space, successively in terms of time or in terms of space, at 180 to 300°C and 0.1 to 1.1 MPa pressure in the presence of fluidized catalyst particles, the heat of the reaction being removed by indirect cooling. 98 to 40% of the total quantity of ethylene fed in are introduced into the zone in which the initial chlorination reaction, for example the oxy-chlorination reaction, takes place, and 2 to 60% of the total quantity of ethylene fed in are introduced into the zone in which the second chlorination reaction, for example the direct chlorination reaction, takes place. The process makes it possible to manufacture the 1,2-dichloroethane required for the production of vinyl chloride in one reaction space, while re-using the hydrogen chloride com-pletely and obtaining readily usable heat and with the reaction following a smooth course.
A process is described for the manufacture of 1,2-dichloroethane by the direct chlorination and oxy-chlorination of ethylene in a common reaction space, successively in terms of time or in terms of space, at 180 to 300°C and 0.1 to 1.1 MPa pressure in the presence of fluidized catalyst particles, the heat of the reaction being removed by indirect cooling. 98 to 40% of the total quantity of ethylene fed in are introduced into the zone in which the initial chlorination reaction, for example the oxy-chlorination reaction, takes place, and 2 to 60% of the total quantity of ethylene fed in are introduced into the zone in which the second chlorination reaction, for example the direct chlorination reaction, takes place. The process makes it possible to manufacture the 1,2-dichloroethane required for the production of vinyl chloride in one reaction space, while re-using the hydrogen chloride com-pletely and obtaining readily usable heat and with the reaction following a smooth course.
Description
~2~ 2 _ 2 -The invention relates to a process for the manu-facture of 1,2-dichloroethane in which ethylene is reacted - in the presence of a catalys-t with hydrogen chloride, inert gases containing oxygen, and chlorine in a common reaction space~
1,2-Dichloroethane has been produced on a large industrial scale now for a number of years. It is chiefly converted into vinyl chloride by thermal cracking, and the latter is in turn the basis of the large-tonnage plastic pol-~vinyl chloride ~his use has made 1,2-dichloroethane into one of the most commonly manufactured aliphatic chlorinated hydrocarbons. A number of different processes are known for its manufacture, most of which s-tart from ethylen~. In general~ the direct addition of elementary chlorine to ethylene is used, the reaction frequently being carried out at temperatures of 40 to about 120~C in the liquid phase, in 1,2 dichloroethane. In a form of this process which is often used, the considerable quantity of heat ~ormed in the addition reaction with chlorine is removed by means of boiling 1,2-dichloroethane. Since the boiling point of 1,2~dichloroethane at normal atmospheric pressure is about 8~C, the level of temperature at which the heat is removed is either insufficient to generate steam, or it is only possible to obtain steam at a low ~2~7 tem~erature and thus a low pressure, and this s-team is only suitable to a limited extent for recovering -the energy containedin it.
In order to effect better utilization o~ the heat formed in the direct addition reaction of chlorine with ethylene, it is known to carry out the reaction in the gas phase in the presQnce of a fluidized catalyst, and to crack the 1,2-dichloroethane formed into vinyl chloride immediately afterwards. The catalyst particles act as heat transfer a~ents in this process, which is carried out at temperatures of 370 to 540C and pressures of up to 2.2 MPa, preferably at 0.45 to 1,85 MPa. m e hydrogen chloride formed in the cracking of 1,2-dichloroethane is used for the oxychlorina-tion of ethylene in a separate apparatus. The 1,2-dichloro-ethane obtained therefrom is recycled into the fluidized bedcracking reactor Disad~antages of the process, such as the formation o~ considerable quantities of ethyl chloride, relatively large proportions of unreacted 1,2-dichloroethane in the -cracked products, dif~iculties in regulating and controllingthe process, and a tendency for undesirable polychlorinated hydrocarbons to be formed and for resinification and coking in the cracking reactor, are stated to be reduced if, ~ instead of, ~or example, dehydrochlorination catalystsl fluidized, non-catalytic solids are used in the reactor.
It is also necessary for the chlorine to be introduced into the ohlorination reaction zone in a controlled manner at a number of differen-t points, in order to reduce the risk of coking This makes it necessary to ins-tal special, rela-3 tively complicated apparatus in the flu~dized bed cracking ~2(;~78()2 ` `
.
reactor. There îs, furthermore, the difficulty ofseparating as completely as possible the ho-t cracked gases from the fluidized, finely divided, solid heat t.ransfer medium, and the disadvantage that it is not possible to use in these processes the tubular cracking furnace for liquid or gaseous 1,2-dichloroethane, which is preferred in industry and enables high throughputs to be obtained.
A process is also known for the manufacture of 1,2-dichloroethane, in which excess ethylene, hydrogen chloride and excess oxygen in the form of air are reacted a~ 180 to 350C and in the presence o~ a known oxychlorin-ation catalys~, by suitably adjusting the ratios of the quantities o~ the starting materials and with a conversion 15 of hydrogen chloride of more than 90%, and, after extrac-ting the unreacted hydrogen chloride by washing and con-densing, as a result o~ this, a large part of the 1,2-dichloroethane formed, the residual gases from this sta~e are reacted in a second stage a~ 80 to 250C and in the presence of an iron-containing catalyst, with 80 to-120 mole % ofchlorine,rela-tivetotheethyleneemployed ~n thisstage.
~ similarproc~ssalso op~rRtesin ~osepar~te stages, between which 1,2-dichloroethane and water are separated out from the reaction product, and the excess ethylene from the oxychlorination reaction is reacted in the second s-tage with chlorine at a temperature of 80 to 320C in the pre-sence of an activated aluminum oxide catalyst.
A recent disclosure is -to reduce the considerable quantities of 2-chloroethanol formed in the subsequent chlorina-tion of the éxcess ethylene from the oxychlorination ~2~7802 : _ 5 -reaction, by carrying out the reaction in the presence of added hydrogen chloride.
Finally, a process is known in which the by-products formed in the chlorination of ethylene-containing gases obtained a~ter the oxychlorination reaction and after removing, by chilling.with water, the bulk of the organic products formed, are reduced by carrying out the chlorina-tion in the presence 9 as a catalyst, of copper(II) chloride and/or iron~III)chloride on a support;
All these last-mentioned processes have the dis-advantage that an additional reactor, equipped with a product separator and further devices, is re~uired in order to improve the yield of 1,2~dichloroethane, relative to the ethylene employed, in the oxychlorination reaction. A pro-1~ cess has now been found, by means of which it is possible to carry out both the oxychlorination and the direct addition OI chlorine to ethylene in a common reaction space, with good yields of 1,2 dichloroethane, and the -temperature level of the reaction makes it possible to utilize the heat which is removed from the addition reaction of chlorine with ethylene in a substantially better manner than in -the process, which has hitherto been used con-siderably9 of chlorination in boiling 1,2-dichloroethane.
The new process for the manufacture o~ 1,2-dichloro-ethane from ethylene by reaction with hydrogen chloride andinert gases containing oxygen, at 180 to 300~C and a pressure of 0.1 to 1.1 MPa, and by reaction with chlorine in the gas phase in the presence of a soli.d catalyst con-taining copper salts or copper and iron salts, with subsequent cooling and ~L2~7l30Z
separation by distillation of the reaction mixture, both chlorination reaction.s being carried out successively in a common reaction space containing fluidized catalyst particles, and the heat formed in the whole reaction space 5 being removed by indirect cooling with a liquid and/or gaseous heat transfer medium, comprises întroducing, into the zone of the reaction space in which the first chlorina-tion reaction takes place, 98 to 40% of the total quantity of the volume o~ ethylene introduced into the common 10 reaction space9 and introducing, into the zone of ihe reaction space in which the second chlorination reaction takes place, the remaining 2 to 60% of the total quantity of the volume of ethylene introduced into the common reaction space 15 The tWQ chlorination reactions can be carried out successively in any desired sequence, 1,2-dichloroethane which is of a high-grade quality being obtained in good yields even if the ~uantity of ethylene reacted in each chlorination s-tage is of approximately the same size The 20 latter process is a preferred variant of the process according to the invention, if the 1,2-dichloroethane pro-duced is subsequently converted into vinyl chloride in the customary manner by thermal cracking, since it is possible in this way to produce, in a single reaction unit and with good utilizat.ion of heat, the total quantity of 1,2-dichloro-ethane to be cracked, the hydrogen chloride produced in the cracking process being recycled to the production of 1,2 dichloroethane and being used to chlorinate about half the total ethylene employed.
~L~0~802 Examples of suitable heat -transfer media for removing by indirect cooling the heat formed in the whole reaotion space are high boiling mineral oils and silicone oils. It is preferable to employ water, which is converted 5 into medium-pressure steam through absorbin~ this heat.
In a preferred embodiment of the process according to the invention the inert gas containing oxygen, an initial fraction of the ethylene and the hydrogen chloride are first introduced into the reaction space, and the 10 second fraction of the ethylene and the chlorine are then introduced, the molar ratios being as follows: 2 moles of HCl; 1.01 to ~ moles of C2H4 (total quantity)i at least 0.5, in general 0.5 to 1, mole of 2 and 0.009 to 2 moles of C12, the quantity of chlorine being such that less than 15 0.001% by ~eight of free, elementary chlorin~ is found in the end product of the reaction, that is to say in the gas mixture leaving the reaction space.
The total quantity of 1.01 to 3 moles of ethylene indicated in the preceding paragraph is divided in such a 20 way that 98 to 40% of this total quantity, preferably 95 to 60~ of this total quantity, are introduced into the reaction space together with the hydrogen chloride or in the imme-diate neigh~orhood of the latter. The remaining 2 to 60%, preferably 5 to 40%, of the total quantity of ethylene are introduced into the reaction space near to, advantageously a little upstream of, the point at which chlorine is intro-duced into the reaction space If 9 for example, the total quantity of ethylene introduced into the reaction space in a specific time is 2 moles, 98 to 40% thereof~ tha-t is -to ~2~7802 _ 8 _ say 1.96 to 0.8 moles, preferably 95 to 60%, that is to say 1.9 to 1.2 moles, of ethylene are introduced together with the hydrogen chloride, and 2 to 60%, that is to say 0.04 to 1.2 moles, preferably 5 to 40%, that is to say 5 0.1 to 0.8 mole, of ethylene are introduced into the reac-tion space a little upstream of the introduction of chlorine. If les~ than 40% of the total quantity of the - ethylene are introduced together with the hydrogen chloride or in the immediate neighborhood of the latter, a decrease 10 in the yield of 1,2-dichloroethane and an increase in the formation of undesirable by-prodùcts is observed.
Inert gas is to be understood as meaning substances which are gaseous under the reaction conditions and which - either take no part at all in the reaction or only do so to 15 a very minor extent. Examples of inert gases are nitrogan, carbon dioxide and 1,2-dichloroethane vapor. Nitrogen is - preferably employed as the inert gas. Thequantity ofinert gas is advantageously such that an adequate fluidization of the solid catalyst particles is achieved without the 20 reaction mixture being diluted unduly.
50 to 100~, in particular 90 to 1005$, of the total ~uantity of oxygen is preferably introduced in-to the reaction space in the form of air.
As far as possible, all the gases are brought into 25 the reaction zone ~ a low relative humidity. The hydrogen chloride gas preferably originates from the thermal crack~ng of 1,2-dichloroethane for the manufacture of vinyl chloride. Before being fed into the reaction space, the gases can be preheated, for example to temperatures of 1~07802 g _ 60 to 180C.
All the gases can be introduced individually into the reaction space, the ethylene in at least two fractions, but it is preferable to introduce hydrogen chloride and an 5 initial fraction of the ethylene on the one hand, and oxygen and an inert gas, for example in the form of air, on -t~e other hand, in each case as mixtures with one another. Chlorine can be introduced into the reaction space at a later -time than the introduction of the other 10 gases in a discontinuous procedure, or downstream of the introduction of the other gases in the preferred continuous procedure. The second fraction of the ethylene is advan-tageously fed into the reaction space a little upstream of - the introduction of the chlorine.
Th reaction space can have, for example, a spherical, ellipsoidal or cylindrical shape; it should be designed in such a way that it does not have any dead corners and angles in which the fluidized catalyst can be deposited. It is preferable to use an elongated cylindrical reaction space having a circular cross-sec-tion and an axis of the cylinder perpendicular thereto, for example a tube.
The reaction space is advantageousl~ equipped with a doùble jacXet and also internal fitments through which the heat transfer medium flows. Examples of suitable internal fitments are coil coolers or calandria coolers.
These in-ternal fitments can be arranged in several units, separated from one another, through which different media can flow at various speeds of flow, in order to make possible optimum utilization of heat and an optimum ~207~(~2 tempera-ture pattern ~ithin the reaction space.
Thc various gases can be introduced into the reaction space through plain pipes which advantageously con-tain, at their ends, devices for improved distribution over the surface area. Examples of suitable devices of this type are perforated plates or spheres, frits or one or several pipes ~aving a plurality of gas outflow aper-tures.
In its top zone, the reaction space advantageously contains an aperture of controllable cross-section, through which the reaction products are removed. After leaving the reaction space, the reaction products advantageously pass through a precipitator for finely divided, solid catalyst particles, for example a cyclone or a similar apparatus The precipitated particles are returned to the reactor.
After leaving the precipitator,the gases are,if appro-priate, washed and partially condensed; the gas fractions which ca~not be condensed at approx. 10C under normal pressure are passed into the atmosphere, if appropriate a~ter removing harmful or objectiona~le subs-tances. At least part of the incondensable gases can also be recycled into the react~on space. me condensed reaction products are separated by distillation in order to obtain pure 1,2-dichloroethane, in the customary manner.
In a particularly preferred embodiment of the presen-t invention, the substances to be reacted are intro~
duced into the reaction space in -the following ratios:
1,2-Dichloroethane has been produced on a large industrial scale now for a number of years. It is chiefly converted into vinyl chloride by thermal cracking, and the latter is in turn the basis of the large-tonnage plastic pol-~vinyl chloride ~his use has made 1,2-dichloroethane into one of the most commonly manufactured aliphatic chlorinated hydrocarbons. A number of different processes are known for its manufacture, most of which s-tart from ethylen~. In general~ the direct addition of elementary chlorine to ethylene is used, the reaction frequently being carried out at temperatures of 40 to about 120~C in the liquid phase, in 1,2 dichloroethane. In a form of this process which is often used, the considerable quantity of heat ~ormed in the addition reaction with chlorine is removed by means of boiling 1,2-dichloroethane. Since the boiling point of 1,2~dichloroethane at normal atmospheric pressure is about 8~C, the level of temperature at which the heat is removed is either insufficient to generate steam, or it is only possible to obtain steam at a low ~2~7 tem~erature and thus a low pressure, and this s-team is only suitable to a limited extent for recovering -the energy containedin it.
In order to effect better utilization o~ the heat formed in the direct addition reaction of chlorine with ethylene, it is known to carry out the reaction in the gas phase in the presQnce of a fluidized catalyst, and to crack the 1,2-dichloroethane formed into vinyl chloride immediately afterwards. The catalyst particles act as heat transfer a~ents in this process, which is carried out at temperatures of 370 to 540C and pressures of up to 2.2 MPa, preferably at 0.45 to 1,85 MPa. m e hydrogen chloride formed in the cracking of 1,2-dichloroethane is used for the oxychlorina-tion of ethylene in a separate apparatus. The 1,2-dichloro-ethane obtained therefrom is recycled into the fluidized bedcracking reactor Disad~antages of the process, such as the formation o~ considerable quantities of ethyl chloride, relatively large proportions of unreacted 1,2-dichloroethane in the -cracked products, dif~iculties in regulating and controllingthe process, and a tendency for undesirable polychlorinated hydrocarbons to be formed and for resinification and coking in the cracking reactor, are stated to be reduced if, ~ instead of, ~or example, dehydrochlorination catalystsl fluidized, non-catalytic solids are used in the reactor.
It is also necessary for the chlorine to be introduced into the ohlorination reaction zone in a controlled manner at a number of differen-t points, in order to reduce the risk of coking This makes it necessary to ins-tal special, rela-3 tively complicated apparatus in the flu~dized bed cracking ~2(;~78()2 ` `
.
reactor. There îs, furthermore, the difficulty ofseparating as completely as possible the ho-t cracked gases from the fluidized, finely divided, solid heat t.ransfer medium, and the disadvantage that it is not possible to use in these processes the tubular cracking furnace for liquid or gaseous 1,2-dichloroethane, which is preferred in industry and enables high throughputs to be obtained.
A process is also known for the manufacture of 1,2-dichloroethane, in which excess ethylene, hydrogen chloride and excess oxygen in the form of air are reacted a~ 180 to 350C and in the presence o~ a known oxychlorin-ation catalys~, by suitably adjusting the ratios of the quantities o~ the starting materials and with a conversion 15 of hydrogen chloride of more than 90%, and, after extrac-ting the unreacted hydrogen chloride by washing and con-densing, as a result o~ this, a large part of the 1,2-dichloroethane formed, the residual gases from this sta~e are reacted in a second stage a~ 80 to 250C and in the presence of an iron-containing catalyst, with 80 to-120 mole % ofchlorine,rela-tivetotheethyleneemployed ~n thisstage.
~ similarproc~ssalso op~rRtesin ~osepar~te stages, between which 1,2-dichloroethane and water are separated out from the reaction product, and the excess ethylene from the oxychlorination reaction is reacted in the second s-tage with chlorine at a temperature of 80 to 320C in the pre-sence of an activated aluminum oxide catalyst.
A recent disclosure is -to reduce the considerable quantities of 2-chloroethanol formed in the subsequent chlorina-tion of the éxcess ethylene from the oxychlorination ~2~7802 : _ 5 -reaction, by carrying out the reaction in the presence of added hydrogen chloride.
Finally, a process is known in which the by-products formed in the chlorination of ethylene-containing gases obtained a~ter the oxychlorination reaction and after removing, by chilling.with water, the bulk of the organic products formed, are reduced by carrying out the chlorina-tion in the presence 9 as a catalyst, of copper(II) chloride and/or iron~III)chloride on a support;
All these last-mentioned processes have the dis-advantage that an additional reactor, equipped with a product separator and further devices, is re~uired in order to improve the yield of 1,2~dichloroethane, relative to the ethylene employed, in the oxychlorination reaction. A pro-1~ cess has now been found, by means of which it is possible to carry out both the oxychlorination and the direct addition OI chlorine to ethylene in a common reaction space, with good yields of 1,2 dichloroethane, and the -temperature level of the reaction makes it possible to utilize the heat which is removed from the addition reaction of chlorine with ethylene in a substantially better manner than in -the process, which has hitherto been used con-siderably9 of chlorination in boiling 1,2-dichloroethane.
The new process for the manufacture o~ 1,2-dichloro-ethane from ethylene by reaction with hydrogen chloride andinert gases containing oxygen, at 180 to 300~C and a pressure of 0.1 to 1.1 MPa, and by reaction with chlorine in the gas phase in the presence of a soli.d catalyst con-taining copper salts or copper and iron salts, with subsequent cooling and ~L2~7l30Z
separation by distillation of the reaction mixture, both chlorination reaction.s being carried out successively in a common reaction space containing fluidized catalyst particles, and the heat formed in the whole reaction space 5 being removed by indirect cooling with a liquid and/or gaseous heat transfer medium, comprises întroducing, into the zone of the reaction space in which the first chlorina-tion reaction takes place, 98 to 40% of the total quantity of the volume o~ ethylene introduced into the common 10 reaction space9 and introducing, into the zone of ihe reaction space in which the second chlorination reaction takes place, the remaining 2 to 60% of the total quantity of the volume of ethylene introduced into the common reaction space 15 The tWQ chlorination reactions can be carried out successively in any desired sequence, 1,2-dichloroethane which is of a high-grade quality being obtained in good yields even if the ~uantity of ethylene reacted in each chlorination s-tage is of approximately the same size The 20 latter process is a preferred variant of the process according to the invention, if the 1,2-dichloroethane pro-duced is subsequently converted into vinyl chloride in the customary manner by thermal cracking, since it is possible in this way to produce, in a single reaction unit and with good utilizat.ion of heat, the total quantity of 1,2-dichloro-ethane to be cracked, the hydrogen chloride produced in the cracking process being recycled to the production of 1,2 dichloroethane and being used to chlorinate about half the total ethylene employed.
~L~0~802 Examples of suitable heat -transfer media for removing by indirect cooling the heat formed in the whole reaotion space are high boiling mineral oils and silicone oils. It is preferable to employ water, which is converted 5 into medium-pressure steam through absorbin~ this heat.
In a preferred embodiment of the process according to the invention the inert gas containing oxygen, an initial fraction of the ethylene and the hydrogen chloride are first introduced into the reaction space, and the 10 second fraction of the ethylene and the chlorine are then introduced, the molar ratios being as follows: 2 moles of HCl; 1.01 to ~ moles of C2H4 (total quantity)i at least 0.5, in general 0.5 to 1, mole of 2 and 0.009 to 2 moles of C12, the quantity of chlorine being such that less than 15 0.001% by ~eight of free, elementary chlorin~ is found in the end product of the reaction, that is to say in the gas mixture leaving the reaction space.
The total quantity of 1.01 to 3 moles of ethylene indicated in the preceding paragraph is divided in such a 20 way that 98 to 40% of this total quantity, preferably 95 to 60~ of this total quantity, are introduced into the reaction space together with the hydrogen chloride or in the imme-diate neigh~orhood of the latter. The remaining 2 to 60%, preferably 5 to 40%, of the total quantity of ethylene are introduced into the reaction space near to, advantageously a little upstream of, the point at which chlorine is intro-duced into the reaction space If 9 for example, the total quantity of ethylene introduced into the reaction space in a specific time is 2 moles, 98 to 40% thereof~ tha-t is -to ~2~7802 _ 8 _ say 1.96 to 0.8 moles, preferably 95 to 60%, that is to say 1.9 to 1.2 moles, of ethylene are introduced together with the hydrogen chloride, and 2 to 60%, that is to say 0.04 to 1.2 moles, preferably 5 to 40%, that is to say 5 0.1 to 0.8 mole, of ethylene are introduced into the reac-tion space a little upstream of the introduction of chlorine. If les~ than 40% of the total quantity of the - ethylene are introduced together with the hydrogen chloride or in the immediate neighborhood of the latter, a decrease 10 in the yield of 1,2-dichloroethane and an increase in the formation of undesirable by-prodùcts is observed.
Inert gas is to be understood as meaning substances which are gaseous under the reaction conditions and which - either take no part at all in the reaction or only do so to 15 a very minor extent. Examples of inert gases are nitrogan, carbon dioxide and 1,2-dichloroethane vapor. Nitrogen is - preferably employed as the inert gas. Thequantity ofinert gas is advantageously such that an adequate fluidization of the solid catalyst particles is achieved without the 20 reaction mixture being diluted unduly.
50 to 100~, in particular 90 to 1005$, of the total ~uantity of oxygen is preferably introduced in-to the reaction space in the form of air.
As far as possible, all the gases are brought into 25 the reaction zone ~ a low relative humidity. The hydrogen chloride gas preferably originates from the thermal crack~ng of 1,2-dichloroethane for the manufacture of vinyl chloride. Before being fed into the reaction space, the gases can be preheated, for example to temperatures of 1~07802 g _ 60 to 180C.
All the gases can be introduced individually into the reaction space, the ethylene in at least two fractions, but it is preferable to introduce hydrogen chloride and an 5 initial fraction of the ethylene on the one hand, and oxygen and an inert gas, for example in the form of air, on -t~e other hand, in each case as mixtures with one another. Chlorine can be introduced into the reaction space at a later -time than the introduction of the other 10 gases in a discontinuous procedure, or downstream of the introduction of the other gases in the preferred continuous procedure. The second fraction of the ethylene is advan-tageously fed into the reaction space a little upstream of - the introduction of the chlorine.
Th reaction space can have, for example, a spherical, ellipsoidal or cylindrical shape; it should be designed in such a way that it does not have any dead corners and angles in which the fluidized catalyst can be deposited. It is preferable to use an elongated cylindrical reaction space having a circular cross-sec-tion and an axis of the cylinder perpendicular thereto, for example a tube.
The reaction space is advantageousl~ equipped with a doùble jacXet and also internal fitments through which the heat transfer medium flows. Examples of suitable internal fitments are coil coolers or calandria coolers.
These in-ternal fitments can be arranged in several units, separated from one another, through which different media can flow at various speeds of flow, in order to make possible optimum utilization of heat and an optimum ~207~(~2 tempera-ture pattern ~ithin the reaction space.
Thc various gases can be introduced into the reaction space through plain pipes which advantageously con-tain, at their ends, devices for improved distribution over the surface area. Examples of suitable devices of this type are perforated plates or spheres, frits or one or several pipes ~aving a plurality of gas outflow aper-tures.
In its top zone, the reaction space advantageously contains an aperture of controllable cross-section, through which the reaction products are removed. After leaving the reaction space, the reaction products advantageously pass through a precipitator for finely divided, solid catalyst particles, for example a cyclone or a similar apparatus The precipitated particles are returned to the reactor.
After leaving the precipitator,the gases are,if appro-priate, washed and partially condensed; the gas fractions which ca~not be condensed at approx. 10C under normal pressure are passed into the atmosphere, if appropriate a~ter removing harmful or objectiona~le subs-tances. At least part of the incondensable gases can also be recycled into the react~on space. me condensed reaction products are separated by distillation in order to obtain pure 1,2-dichloroethane, in the customary manner.
In a particularly preferred embodiment of the presen-t invention, the substances to be reacted are intro~
duced into the reaction space in -the following ratios:
2 moles of HCl; 1 8 to 2.2 moles of C2H4 (-total quantity);
0.5 to 0.6 mole of 2 and 0.79 to 1 2 mole of C12, the 1.2~7802 11 _ quantity of chlorine being such that less than 0.001% by weight of free, elementary chlorine is found in the gas mixture leaving the reaction space~ If these molar ratios are used, 1,2-dichloroethane can be produced in a single 5 reaction unit for the subsequent cracking to give vinyl chloride, ~ith optimum utilization of the hydrogen chloride which is returned from the cracking process and of the starting materials ethylene and chlorine.
. As described above 9 the total quantity of 1.8 to 10 2.2 moles of ethylene is divided in such a way that 98 to 4~% of this total quantity, preferably 95 to 60% of this total quantity, is introduced into the reaction space toge-ther with the hydrogen chloride or in the immediate neighborhood of the latter~ The remaining 2 t.o ~0%, pre-- 15 ferably 5 to 40%, of the total quanti-ty of e~hylene are fed into the reaction space near to, advantageously a little upstream of, the point at ~hich chlorine is intro-duced into the reaction space The process described in the two preceding para~
20 graphs iS9 in particular, carrièd out in such a way that an initial fraction of the ethylene, hydrogen chloride and oxygen-containing inert gas are introduced separately, or at least in part separately, from one another at one end - of a tubular reactor, advantageously at the lower end o~
25 a vertical or nearly vertical tubular reactor. For example, the initial fraction of the ethylene and hydrogen chloride can be introduced together, but separately from the oxygen-containing iner-t gas. Chlorine and, advantageously a little ups-tream thereof, the second fraction of the 12~7802 _ 12 _ ethylene are introduced into the reaction space at a point separated by specific distance from the last of the above-mentioned gas inlets in the direction of flow of the gas.
The position of the chlorine inlet is selected so that there is a reaction space amounting to 40 to 85%, prefer-ably 55 to 75%, of the total available reaction space in the reactor between this inlet and the preceding hydrogen chloride inlet. The reaction products are removed at the - other end of the reactor, advantageously at the top of a vertical or nearly vertical tubular reactorO
A process of this type is particularly suitable for continuous operation, which is important in industry.
For this continuous operation, in which, in the direction of flow of the gases, hydrogen chloride is introduced first and chlorine is ir.troduced subsequently, the heat transfer medium in -the indirect cooling of the reaction space is preferably passed counter-current to the gases within the reaction space A better removal of heat and a n~ore advantageous temperature pattern within the reaction space are achieved by this means.
In a further preferred embodiment of the process according to the invention, first inert gas, which can,ifa~o-priate, contain oxygen, and an initial fraction of the ethylene and, separate therefrom, chlorine and subsequently hydrogen chloride, the second frac-tion of the ethylene and, if appropriate, oxygen and inert gas are introduced into the reaction space in the following molar ratios: 2 moles of C2E~4 (total quan-tity); 0.9 to 1.2 moles of C12; 1.6 to 2 3 moles o~ HCl and 0.35 to 1 3 moles o~ total 2~ the 7~0Z
~uantity of oxygen or of hydrogen chloride being such that l~ss than 0.001% by weight of free, elementary chlorine is found in the end product, that is to say in the gas mixture leaving the reaction space.
The ~otal of 2 moles o~ ethylene in-troduced ~lithin a specific period are divided in such a way -that 98 to 4~%
of this total quantity are introduced into the reaction space in the immediate neighborhood of the chlorine inlet.
The remaining 2 to 60% of the to-tal quantity of ethylene are fed into the reaction space either together with the hydrogen chloride or in the immediate neighborhood of the latter.
This embodiment of the process is used partlcularly when the process is to be carried out ~ith a small excess of hydrogen chloride, for example in order to reduce the proportion of 2-chloroethanol in the reaction product.
As already described above, this embodiment is also suit-able for producing 1,2-dichloroethane for thermal cracking to give vinyl chloride, with opti~l~ utilization of the hydrogen chloride produced in this cracking reaction, -the total production oP 1,2-dichloroethane taking place in a single reaction space Examples of suitable inert gases are, once again, as described above~ nitrogen~ carbon dioxide and/or 1,2-dichloroethane vapor, nitrogen being employed preferentiallyme bulk of the oxygen required is advantageously supplied at the point at ~hich the hydrogen chloride is also intro-~uced, but it is also possible to supply considerable ~uantities of oxygen as far back as the point a-t which an initial fraction o~ the e-thylene, and the chlorine are introduced. This procedure is used particularly ~hen it is desired to employ air as a low-cost fluidization gas The process described in the four preceding para-graphs is, in particular, carried out in such a way that an initial fraction of the ethylene 9 chlorine and inert gas, which can, if appropriate, contain oxygen, are intro-duced, separate from oneanotherat leastin part,advantageously atthebottomofavertical ornearlyver~icaltubular reactor.
The inert gas can, for example, also be introduced as a mixture with chlorine, but with the initial ~raction of the ethylene separated therefrom. Hydrogen chloride and, if appropriate~ oxygen and inert gas are introduced into the reaction space separately, or at least in part separ- -ately, at a point separated by a specific distance fromthe last of the abovementioned gas inlets in the direction of flow of the gas. The positivn Qf the hydrogen chloride inlet is selected in such a way that there is a reaction ~` space amounting to 10 to 40%, preferably 15 to 30S', of the total available reaction space in the reactor between this point and the preceding chlorine inlet. The second frac~
tion of the ethylene is introduced into the reaction space together with the hydrogen chloride or in the immediate neighborhood of the latter. The reaction pro~ucts are removed at the other end of the reactor, advantageously at the top o~ a vertical or nearly vertical -tubular reactor.
In the embodiment o~ the new process which has just been described, the heat transfer medium in the indirec-t cooling o~ the reaction space is advantageously passed 12~78~2 co-current to the gases.
The process according to the invention is advan-tageously carried out at temperatures9 of the reaction mix-l~vre in the reaction space, of 190 to 250C, in particular 200 to Z~0C. A spatial temperature gradient can be used, particularly in the case of continuous processes. For example, there can be a lower temperature at the point where the gases are introduced into the reaction space than at the point where the reaction products are taken off. The temperature in the first third of the reac-tion space, viewed in the direction of ~low of the gases, or in the center or in the second third can be higher than in the remaining zones of the reaction space.
The gases are advantageously warmed to temperatures of 50 to about 180C be~ore being introduced into the reaction space~ ~
The new process can be carried out under normal atmospheric pressure (0.09 to 0.1 MPa). In general, an increased pressure of up to about 1.1 MPa will be used in order to increase the space-time yield. It is preferable `
to carry out the reaction at pressures of 0.3 to 0~6 MPa.
The solid catalyst is advantageously used in a ~inely divided form having an average particle size of 20 to ~0 ~m~ Particularly good results are obtained using a catalyst having an average particle size of ~0 to 70 ~m.
The catalyst is advantageously composed of a supporting substance which has a large sur~ace area per unit weigh-t, ~or example 70 to 200 m2/g or moIe, is mechani-cally stable at high temperatures, for example up to a-t ~2~7802 6 ~
least 500C, and emerges unchanged from the gas reaction.
Suitable support materials are heat-stable oxides, for exanple silicon dioxide or al-~inum oxide and also diatomaceous earth or silica-te materials. It is preferable to employ aluminum oxide.
About 0.5 to 15% by weight, relative to the total catalyst, of copper in the form of a salt or oxide is advantageously applied to this support material These copper salts or oxides are generally converted during use into copper(II) chloride by the hydrogen chloride and chlorine present, i~ ~hey have ~not already been applied in the form of this chloride from the start.
Besides copper1 the catalyst can advantageously also contain minor quantities of Lewis acids,in particular about 0.01 to 0.5% by weight, relative to the to-tal catalyst, o~ iron, which has been applied in the ~orm of an oxide or salt and which is converted during the reaction into the Lewis acid iron(III) chloride. me abovementioned per-centages relate in each case to the metal ion, not to the chloride or other metal salt or oxide, Besides the additives mentioned, the catalyst can also contain further additives which reduce the volatility, in particular, of the copper(II~ chloride, for example alkali metal chlorides, such as potassium chloride, or alkaline earth metal chlorides, such as calcium chloride or magnesium chloride, and also additives composed of further metallic compounds which improve the activity and/or selectiYity of the catalyst in respect of -the pro~
duction of 1,2~dichloroethane. Examples which may be ` 17 mentioned are silver, zinc, chromium, manganese, rare earth metals, such as cerium, lanthanum, ytterbium and neodymium, and platinum me-tals, such as rhodium and platinum.
It is also possible to use mixtures of dif~erent catalyst and catalyst support particles, for example support material which has been treated with copper salts, mixed with particles of the untreated support material or of a support material which has been treated differently, for example with iron(IIl) chloride or with another Lewis acid.
The ratio of the total reaction space before charging the catalyst to the apparent volume of the cata-lyst charged is advantageously about l.l~to 3, pre~erably 1.2 to 1.7 The flow rate of the gases in the reaction space is advantageously sufficiently high for at least 95~ by weight, preferably 100~' by weight, of the catalyst particles to become fluidized. The rate at which ~he inert gas, ~hich may be recycled, is fed in 5hould be selected accordingly, taking account of the gases which take part in the reaction and are fed into -the reaction space The average residence time of the reacting gases in the reaction space depends on the reaction temperature selected, and in general -there should be a shorter resi-dence time if the reaction temperature is adjusted to a higher value~ ~le average residence time is generally 10 ~o 100? preferably 2Q to 70, seconds, in particular 30 to 60 seconds. In continuous operation, the residence time -` ~Z~7~
- 18 _ is determined from the volume of the gases fed into the reaction space per second under the pressure and at the temperature prevailing in the reaction space, rela-tive to the volume of the total reaction space, less the -true volume of the catalyst contained therein and of the inter-nal fitments (cooling tubes and temperature sensor). The true volume of the catalyst particles is determined, for - example, by the method of liquid displacement (see later in the text).
In the process according to the invention, it is preferable to introduce sufficient oxygen, or inert gas containing oxygen, into the reaction spaoe for the gas mixture leaving the reaction space still lo contain 2 to 9, in particular 4 to 7, % by vQlume of oxygen, after the readily condensable reaction products ~for exam~le water and 1,2-dichloroethane) have been condensed at +10C and after the hydrogen chloride has been removed by conven-tional washing. In regard to washing ~he exit gases ~rith combustible organic solvents in order to remove residual quantities o~ 1,2-dichloroethanè~ it is advantageous, ~or example, if the 2 content of the exit gas ~hich has been pretreated as described above is not too high, for example is less than 9~0 by volume. If a subsequent purification of this type is not envisaged, it is also possible for the oxygen content to be even higher, for example 10 to 13% by volu~e, it being still possible to achieve very good yields of 1,2-dichloroethane As already described earlier in the text, the separation and purification of the gas mixsture leaving the .
0~
reaction space is ef~ected by known processes As also already indicated above, the process according -to the invention makes it possible, on the one hand, to react ethylene, in a single reaction unit and in 5 a particularly good yield to give 1,2~dichloroethane of good auality, by oxychlorinating the bulk of the ethylene and subsequent chlorination of the remainder of the ethylene. On the other hand, the new process makes it possible, using only one reaction unit, to produce the 10 total quantity of 1,2-dichloroethane in a good quality and yield for the subsequent thermal decomposition for the production of vinyl chloride~ with substantially com-plete re-use of the hydrogen chloride produced in the ther-mal decomposition. A considerable quantity of heat is formed in the reaction uni.t at a level of temperature which makes it possible to re use this heat under advantageous conditions, for example as medium-pressure steam. The pro-cess does not require any complicated or capital-intensive apparatus or apparatus susceptible to trouble, and it can 20 be carried out in equipment which is easy to clean and to maintain.
The distribution of the introduction of ethylene into -the reaction spaoe makes it possible to maintain a more uniform temperature and -thus to control the course of the reaction in an improved manner.
The following examples are intended to illustrate the invention in greater de-tail:
E~amples 1 to 7 The follow.ing appara-tus is.used: the conversion ~Z~713~Z
_ 20 -of ethylene into 1,2-dichloroethane is carried out using a vertical glass tube of internal diameter 80 ~m which is narrowed at the bottom and at the top to form in the one case a gas inflow aperture ~nd in the other case a gas out-5 flow aperture. Immediately above the bottom inflow aper-~ ture, this vertical reaction tube contains a glass frit ~hich covers the ~hole internal cross~section o~ the reaction tube. A second frit is fitted a short distance above this first frit and has a surface area amounting to about hal~ the cross-section of the reaction tube and is attached, in its lower part, to a glass tube which passes through the side of the jacket of the reaction -tube.
In order to control the temperature, the reaction tube con-tains a coiled glass tube, the connections to which also pass through the side of the jacket of the reaction tube, and which begins a little way above the second frit and extends upwards in the reaction tube sufficiently far for about 1/10 of the total length of -the reaction tube in the upper section to remain free. 4 sockets, through which temperature sensors extend into the interior of the reac-tion tube, are fitted between the second frit and the top end of the reaction tube, distributed uniformly over the jacket o~ the tube. At specific distances above frit 2, --the jacket of the reaction -tube contains three further sockets~ through which i-t is possible to carry gas inlet tubes ~Yhich extend into the center of the reac-tion tube, are bent vertically do~mwards there and end in a perforated sphere. If a gas inlet tube is carried through -the socket (A) which is ~itted at the greatest distance from -the second .
12~ 02 _ 2~ _ frit, the distance between the perforated sphere and the sccond frit is 69% of the total internal length of the reaction space in the reaction -tube. The reaction space is measured from the surfacç of the first frit to the point 5 ~lhere the top section of the reaction tube narrows. If a gas inlet tube is carried through the socket (C) which is nearest to the second frit, the distance from the per-forated sphere of the gas inlet tube to the second frit is 17% of the total length of the reaction space in the reaction tube. If a gas inlet tube is carried through the socket (B) which is between the two sockets just described, the distance from the perforated sphere of the gas inlet tube to the second frit is 53% of the total length of the reaction space in the reaction tube, The whole mantel of the reaction t~be is provided with a heat insulating layer.
A glass sphere is fitted above the reaction tube in order to precipitate catalyst particles which have been entrained by the gas stream. This glass sphere is in turn connected via a descending line to a water condenser, at the lower end oP which a condensate receiver equipped with a drain cock is attached, In its upper section, the con-densate receiver contains a gas exit tube which in turn leads into an ascending brine cooler~ The constituents of the gas which are condensed here flow into a second con-densate receiver equipped ~ith a drain cock. The incon-dens~ble exit gases leaving the upper section of the brine cooler are passed through wash bottles in order to remove -the hydrogen chloride contained in them. Samples of the ~ashed exit gas are taken for analysis by gas chromatography.
- ~ 1207~30:2 . 22 The condensates which are collected in the two vessels moun-ted below the condenser are combined and are also analyzed by gas chromatography.
The glass sphere in which the entrained catalyst particles are precipitated and the connecting tube leading from it to the water condenser are provided with electri-cally heated sleeves. During the operation of the reactor, these parts o~ the apparatus are heated sufficiently for no ~ormation of condensate to take place in them The volume of the reaction space in the reaction tube~ less the internal fitments contained therein (tem-perature control coil, second ~rit, gas inlet sphere and ~emperature sensor) is 4,700 cm3.
For carrying out the first example, the reaction tube is charged with 2.8 dm3 (apparent vol~e) of a catalyst which is composed of an aluminum oxide support and contains
0.5 to 0.6 mole of 2 and 0.79 to 1 2 mole of C12, the 1.2~7802 11 _ quantity of chlorine being such that less than 0.001% by weight of free, elementary chlorine is found in the gas mixture leaving the reaction space~ If these molar ratios are used, 1,2-dichloroethane can be produced in a single 5 reaction unit for the subsequent cracking to give vinyl chloride, ~ith optimum utilization of the hydrogen chloride which is returned from the cracking process and of the starting materials ethylene and chlorine.
. As described above 9 the total quantity of 1.8 to 10 2.2 moles of ethylene is divided in such a way that 98 to 4~% of this total quantity, preferably 95 to 60% of this total quantity, is introduced into the reaction space toge-ther with the hydrogen chloride or in the immediate neighborhood of the latter~ The remaining 2 t.o ~0%, pre-- 15 ferably 5 to 40%, of the total quanti-ty of e~hylene are fed into the reaction space near to, advantageously a little upstream of, the point at ~hich chlorine is intro-duced into the reaction space The process described in the two preceding para~
20 graphs iS9 in particular, carrièd out in such a way that an initial fraction of the ethylene, hydrogen chloride and oxygen-containing inert gas are introduced separately, or at least in part separately, from one another at one end - of a tubular reactor, advantageously at the lower end o~
25 a vertical or nearly vertical tubular reactor. For example, the initial fraction of the ethylene and hydrogen chloride can be introduced together, but separately from the oxygen-containing iner-t gas. Chlorine and, advantageously a little ups-tream thereof, the second fraction of the 12~7802 _ 12 _ ethylene are introduced into the reaction space at a point separated by specific distance from the last of the above-mentioned gas inlets in the direction of flow of the gas.
The position of the chlorine inlet is selected so that there is a reaction space amounting to 40 to 85%, prefer-ably 55 to 75%, of the total available reaction space in the reactor between this inlet and the preceding hydrogen chloride inlet. The reaction products are removed at the - other end of the reactor, advantageously at the top of a vertical or nearly vertical tubular reactorO
A process of this type is particularly suitable for continuous operation, which is important in industry.
For this continuous operation, in which, in the direction of flow of the gases, hydrogen chloride is introduced first and chlorine is ir.troduced subsequently, the heat transfer medium in -the indirect cooling of the reaction space is preferably passed counter-current to the gases within the reaction space A better removal of heat and a n~ore advantageous temperature pattern within the reaction space are achieved by this means.
In a further preferred embodiment of the process according to the invention, first inert gas, which can,ifa~o-priate, contain oxygen, and an initial fraction of the ethylene and, separate therefrom, chlorine and subsequently hydrogen chloride, the second frac-tion of the ethylene and, if appropriate, oxygen and inert gas are introduced into the reaction space in the following molar ratios: 2 moles of C2E~4 (total quan-tity); 0.9 to 1.2 moles of C12; 1.6 to 2 3 moles o~ HCl and 0.35 to 1 3 moles o~ total 2~ the 7~0Z
~uantity of oxygen or of hydrogen chloride being such that l~ss than 0.001% by weight of free, elementary chlorine is found in the end product, that is to say in the gas mixture leaving the reaction space.
The ~otal of 2 moles o~ ethylene in-troduced ~lithin a specific period are divided in such a way -that 98 to 4~%
of this total quantity are introduced into the reaction space in the immediate neighborhood of the chlorine inlet.
The remaining 2 to 60% of the to-tal quantity of ethylene are fed into the reaction space either together with the hydrogen chloride or in the immediate neighborhood of the latter.
This embodiment of the process is used partlcularly when the process is to be carried out ~ith a small excess of hydrogen chloride, for example in order to reduce the proportion of 2-chloroethanol in the reaction product.
As already described above, this embodiment is also suit-able for producing 1,2-dichloroethane for thermal cracking to give vinyl chloride, with opti~l~ utilization of the hydrogen chloride produced in this cracking reaction, -the total production oP 1,2-dichloroethane taking place in a single reaction space Examples of suitable inert gases are, once again, as described above~ nitrogen~ carbon dioxide and/or 1,2-dichloroethane vapor, nitrogen being employed preferentiallyme bulk of the oxygen required is advantageously supplied at the point at ~hich the hydrogen chloride is also intro-~uced, but it is also possible to supply considerable ~uantities of oxygen as far back as the point a-t which an initial fraction o~ the e-thylene, and the chlorine are introduced. This procedure is used particularly ~hen it is desired to employ air as a low-cost fluidization gas The process described in the four preceding para-graphs is, in particular, carried out in such a way that an initial fraction of the ethylene 9 chlorine and inert gas, which can, if appropriate, contain oxygen, are intro-duced, separate from oneanotherat leastin part,advantageously atthebottomofavertical ornearlyver~icaltubular reactor.
The inert gas can, for example, also be introduced as a mixture with chlorine, but with the initial ~raction of the ethylene separated therefrom. Hydrogen chloride and, if appropriate~ oxygen and inert gas are introduced into the reaction space separately, or at least in part separ- -ately, at a point separated by a specific distance fromthe last of the abovementioned gas inlets in the direction of flow of the gas. The positivn Qf the hydrogen chloride inlet is selected in such a way that there is a reaction ~` space amounting to 10 to 40%, preferably 15 to 30S', of the total available reaction space in the reactor between this point and the preceding chlorine inlet. The second frac~
tion of the ethylene is introduced into the reaction space together with the hydrogen chloride or in the immediate neighborhood of the latter. The reaction pro~ucts are removed at the other end of the reactor, advantageously at the top o~ a vertical or nearly vertical -tubular reactor.
In the embodiment o~ the new process which has just been described, the heat transfer medium in the indirec-t cooling o~ the reaction space is advantageously passed 12~78~2 co-current to the gases.
The process according to the invention is advan-tageously carried out at temperatures9 of the reaction mix-l~vre in the reaction space, of 190 to 250C, in particular 200 to Z~0C. A spatial temperature gradient can be used, particularly in the case of continuous processes. For example, there can be a lower temperature at the point where the gases are introduced into the reaction space than at the point where the reaction products are taken off. The temperature in the first third of the reac-tion space, viewed in the direction of ~low of the gases, or in the center or in the second third can be higher than in the remaining zones of the reaction space.
The gases are advantageously warmed to temperatures of 50 to about 180C be~ore being introduced into the reaction space~ ~
The new process can be carried out under normal atmospheric pressure (0.09 to 0.1 MPa). In general, an increased pressure of up to about 1.1 MPa will be used in order to increase the space-time yield. It is preferable `
to carry out the reaction at pressures of 0.3 to 0~6 MPa.
The solid catalyst is advantageously used in a ~inely divided form having an average particle size of 20 to ~0 ~m~ Particularly good results are obtained using a catalyst having an average particle size of ~0 to 70 ~m.
The catalyst is advantageously composed of a supporting substance which has a large sur~ace area per unit weigh-t, ~or example 70 to 200 m2/g or moIe, is mechani-cally stable at high temperatures, for example up to a-t ~2~7802 6 ~
least 500C, and emerges unchanged from the gas reaction.
Suitable support materials are heat-stable oxides, for exanple silicon dioxide or al-~inum oxide and also diatomaceous earth or silica-te materials. It is preferable to employ aluminum oxide.
About 0.5 to 15% by weight, relative to the total catalyst, of copper in the form of a salt or oxide is advantageously applied to this support material These copper salts or oxides are generally converted during use into copper(II) chloride by the hydrogen chloride and chlorine present, i~ ~hey have ~not already been applied in the form of this chloride from the start.
Besides copper1 the catalyst can advantageously also contain minor quantities of Lewis acids,in particular about 0.01 to 0.5% by weight, relative to the to-tal catalyst, o~ iron, which has been applied in the ~orm of an oxide or salt and which is converted during the reaction into the Lewis acid iron(III) chloride. me abovementioned per-centages relate in each case to the metal ion, not to the chloride or other metal salt or oxide, Besides the additives mentioned, the catalyst can also contain further additives which reduce the volatility, in particular, of the copper(II~ chloride, for example alkali metal chlorides, such as potassium chloride, or alkaline earth metal chlorides, such as calcium chloride or magnesium chloride, and also additives composed of further metallic compounds which improve the activity and/or selectiYity of the catalyst in respect of -the pro~
duction of 1,2~dichloroethane. Examples which may be ` 17 mentioned are silver, zinc, chromium, manganese, rare earth metals, such as cerium, lanthanum, ytterbium and neodymium, and platinum me-tals, such as rhodium and platinum.
It is also possible to use mixtures of dif~erent catalyst and catalyst support particles, for example support material which has been treated with copper salts, mixed with particles of the untreated support material or of a support material which has been treated differently, for example with iron(IIl) chloride or with another Lewis acid.
The ratio of the total reaction space before charging the catalyst to the apparent volume of the cata-lyst charged is advantageously about l.l~to 3, pre~erably 1.2 to 1.7 The flow rate of the gases in the reaction space is advantageously sufficiently high for at least 95~ by weight, preferably 100~' by weight, of the catalyst particles to become fluidized. The rate at which ~he inert gas, ~hich may be recycled, is fed in 5hould be selected accordingly, taking account of the gases which take part in the reaction and are fed into -the reaction space The average residence time of the reacting gases in the reaction space depends on the reaction temperature selected, and in general -there should be a shorter resi-dence time if the reaction temperature is adjusted to a higher value~ ~le average residence time is generally 10 ~o 100? preferably 2Q to 70, seconds, in particular 30 to 60 seconds. In continuous operation, the residence time -` ~Z~7~
- 18 _ is determined from the volume of the gases fed into the reaction space per second under the pressure and at the temperature prevailing in the reaction space, rela-tive to the volume of the total reaction space, less the -true volume of the catalyst contained therein and of the inter-nal fitments (cooling tubes and temperature sensor). The true volume of the catalyst particles is determined, for - example, by the method of liquid displacement (see later in the text).
In the process according to the invention, it is preferable to introduce sufficient oxygen, or inert gas containing oxygen, into the reaction spaoe for the gas mixture leaving the reaction space still lo contain 2 to 9, in particular 4 to 7, % by vQlume of oxygen, after the readily condensable reaction products ~for exam~le water and 1,2-dichloroethane) have been condensed at +10C and after the hydrogen chloride has been removed by conven-tional washing. In regard to washing ~he exit gases ~rith combustible organic solvents in order to remove residual quantities o~ 1,2-dichloroethanè~ it is advantageous, ~or example, if the 2 content of the exit gas ~hich has been pretreated as described above is not too high, for example is less than 9~0 by volume. If a subsequent purification of this type is not envisaged, it is also possible for the oxygen content to be even higher, for example 10 to 13% by volu~e, it being still possible to achieve very good yields of 1,2-dichloroethane As already described earlier in the text, the separation and purification of the gas mixsture leaving the .
0~
reaction space is ef~ected by known processes As also already indicated above, the process according -to the invention makes it possible, on the one hand, to react ethylene, in a single reaction unit and in 5 a particularly good yield to give 1,2~dichloroethane of good auality, by oxychlorinating the bulk of the ethylene and subsequent chlorination of the remainder of the ethylene. On the other hand, the new process makes it possible, using only one reaction unit, to produce the 10 total quantity of 1,2-dichloroethane in a good quality and yield for the subsequent thermal decomposition for the production of vinyl chloride~ with substantially com-plete re-use of the hydrogen chloride produced in the ther-mal decomposition. A considerable quantity of heat is formed in the reaction uni.t at a level of temperature which makes it possible to re use this heat under advantageous conditions, for example as medium-pressure steam. The pro-cess does not require any complicated or capital-intensive apparatus or apparatus susceptible to trouble, and it can 20 be carried out in equipment which is easy to clean and to maintain.
The distribution of the introduction of ethylene into -the reaction spaoe makes it possible to maintain a more uniform temperature and -thus to control the course of the reaction in an improved manner.
The following examples are intended to illustrate the invention in greater de-tail:
E~amples 1 to 7 The follow.ing appara-tus is.used: the conversion ~Z~713~Z
_ 20 -of ethylene into 1,2-dichloroethane is carried out using a vertical glass tube of internal diameter 80 ~m which is narrowed at the bottom and at the top to form in the one case a gas inflow aperture ~nd in the other case a gas out-5 flow aperture. Immediately above the bottom inflow aper-~ ture, this vertical reaction tube contains a glass frit ~hich covers the ~hole internal cross~section o~ the reaction tube. A second frit is fitted a short distance above this first frit and has a surface area amounting to about hal~ the cross-section of the reaction tube and is attached, in its lower part, to a glass tube which passes through the side of the jacket of the reaction -tube.
In order to control the temperature, the reaction tube con-tains a coiled glass tube, the connections to which also pass through the side of the jacket of the reaction tube, and which begins a little way above the second frit and extends upwards in the reaction tube sufficiently far for about 1/10 of the total length of -the reaction tube in the upper section to remain free. 4 sockets, through which temperature sensors extend into the interior of the reac-tion tube, are fitted between the second frit and the top end of the reaction tube, distributed uniformly over the jacket o~ the tube. At specific distances above frit 2, --the jacket of the reaction -tube contains three further sockets~ through which i-t is possible to carry gas inlet tubes ~Yhich extend into the center of the reac-tion tube, are bent vertically do~mwards there and end in a perforated sphere. If a gas inlet tube is carried through -the socket (A) which is ~itted at the greatest distance from -the second .
12~ 02 _ 2~ _ frit, the distance between the perforated sphere and the sccond frit is 69% of the total internal length of the reaction space in the reaction -tube. The reaction space is measured from the surfacç of the first frit to the point 5 ~lhere the top section of the reaction tube narrows. If a gas inlet tube is carried through the socket (C) which is nearest to the second frit, the distance from the per-forated sphere of the gas inlet tube to the second frit is 17% of the total length of the reaction space in the reaction tube. If a gas inlet tube is carried through the socket (B) which is between the two sockets just described, the distance from the perforated sphere of the gas inlet tube to the second frit is 53% of the total length of the reaction space in the reaction tube, The whole mantel of the reaction t~be is provided with a heat insulating layer.
A glass sphere is fitted above the reaction tube in order to precipitate catalyst particles which have been entrained by the gas stream. This glass sphere is in turn connected via a descending line to a water condenser, at the lower end oP which a condensate receiver equipped with a drain cock is attached, In its upper section, the con-densate receiver contains a gas exit tube which in turn leads into an ascending brine cooler~ The constituents of the gas which are condensed here flow into a second con-densate receiver equipped ~ith a drain cock. The incon-dens~ble exit gases leaving the upper section of the brine cooler are passed through wash bottles in order to remove -the hydrogen chloride contained in them. Samples of the ~ashed exit gas are taken for analysis by gas chromatography.
- ~ 1207~30:2 . 22 The condensates which are collected in the two vessels moun-ted below the condenser are combined and are also analyzed by gas chromatography.
The glass sphere in which the entrained catalyst particles are precipitated and the connecting tube leading from it to the water condenser are provided with electri-cally heated sleeves. During the operation of the reactor, these parts o~ the apparatus are heated sufficiently for no ~ormation of condensate to take place in them The volume of the reaction space in the reaction tube~ less the internal fitments contained therein (tem-perature control coil, second ~rit, gas inlet sphere and ~emperature sensor) is 4,700 cm3.
For carrying out the first example, the reaction tube is charged with 2.8 dm3 (apparent vol~e) of a catalyst which is composed of an aluminum oxide support and contains
3.7% by weight, relative to the catalyst, of copper in the form of a salt, and traces of iron The catalyst has the following sie~e anal~sis:
Particles ~20 ~ 25% by weight Par-ticles >20 ~, but <70 ~ 65% by weight Particles ~70 ~ 10% by weight.
T~e true volume of the catalyst is determined - by the method of water displacement: a measuring cylinder of 2 dm3 capacity is first filled with 1 dm3 of catalys-t particles and 1 dm3 of water at 20C is added.- The mixture is shaken somewhat and allowed to stand for some time until no more gas bubbles ascend. The volume of the mix-ture iS llOW 1,300 cm3. 1 dm3 (apparent ~olume~ of -the ca-talyst ~2~ 7 _ 23_ thus has a true volume of catalyst particles of 300 cm3.
The whole catalyst charge of 2 8 dm3 has a true volume of 840 cm3. After charging the catalyst, the free gas space in the reaction tube still has a vo]ume of 3.86 dm3.
Air is now blown via the bottom gas inlet tube through the firs-t frit at a rate of 60 standard dm3 per hour and the temperature control coil in the reaction tube is heated by means of a heating fluid. An air temperature of 185C, which does not alter further in the course of the next 5 minutes, is measured in the reaction tube after about 25 minutes. The rate at which air is blown in is now raised to 90 Ndm3 x hours 1 and, at the same time9 a mixture of ethylene, at the rate indicated later in the text, and 44 Ndm3 x hours 1 of hydrogen chloride gas is introduced via the second frit. I~media-tely after this, the intro-duction of 22 Ndm3 x hours 1 of chlorine gas is also com-menced, via the gas inlet tube which is equipped with -the sphere and which is fitted in the socket (A) at the greatest distance from the second frit; at the s~le time ethylene is ~ed into the reaction tube, at the rate indicated later in the tex-t, through the gas inlet tube which is equipped with a sphere and is fitted in the central socket (B).
(The socket nearest to the second frit is not used and is closed ~rith a plug). All the gases fed to the reac-tion tube are preheated to 60C.
In the individual examples, a total of 44.5 Ndm3 x hours 1 of ethylene was passed into the reaction tube in each case, i.n the following fractions, through the two inle-t poin-ts (the second frlt and socket B):
.
Ex E~hylene via: % of the -total quàntity of ~ second socket e-thylene ample frit B firs-t frac-tion second fraction Ndm3.hrs 1 Ndm3.hrs 1 secOndifrit soc,ket B
.
1 4~.4 1.1 97.5 2 5 - 2 38.9 5.6 87.4 12.6 3 33.4 11.1 75.0 25.0
Particles ~20 ~ 25% by weight Par-ticles >20 ~, but <70 ~ 65% by weight Particles ~70 ~ 10% by weight.
T~e true volume of the catalyst is determined - by the method of water displacement: a measuring cylinder of 2 dm3 capacity is first filled with 1 dm3 of catalys-t particles and 1 dm3 of water at 20C is added.- The mixture is shaken somewhat and allowed to stand for some time until no more gas bubbles ascend. The volume of the mix-ture iS llOW 1,300 cm3. 1 dm3 (apparent ~olume~ of -the ca-talyst ~2~ 7 _ 23_ thus has a true volume of catalyst particles of 300 cm3.
The whole catalyst charge of 2 8 dm3 has a true volume of 840 cm3. After charging the catalyst, the free gas space in the reaction tube still has a vo]ume of 3.86 dm3.
Air is now blown via the bottom gas inlet tube through the firs-t frit at a rate of 60 standard dm3 per hour and the temperature control coil in the reaction tube is heated by means of a heating fluid. An air temperature of 185C, which does not alter further in the course of the next 5 minutes, is measured in the reaction tube after about 25 minutes. The rate at which air is blown in is now raised to 90 Ndm3 x hours 1 and, at the same time9 a mixture of ethylene, at the rate indicated later in the text, and 44 Ndm3 x hours 1 of hydrogen chloride gas is introduced via the second frit. I~media-tely after this, the intro-duction of 22 Ndm3 x hours 1 of chlorine gas is also com-menced, via the gas inlet tube which is equipped with -the sphere and which is fitted in the socket (A) at the greatest distance from the second frit; at the s~le time ethylene is ~ed into the reaction tube, at the rate indicated later in the tex-t, through the gas inlet tube which is equipped with a sphere and is fitted in the central socket (B).
(The socket nearest to the second frit is not used and is closed ~rith a plug). All the gases fed to the reac-tion tube are preheated to 60C.
In the individual examples, a total of 44.5 Ndm3 x hours 1 of ethylene was passed into the reaction tube in each case, i.n the following fractions, through the two inle-t poin-ts (the second frlt and socket B):
.
Ex E~hylene via: % of the -total quàntity of ~ second socket e-thylene ample frit B firs-t frac-tion second fraction Ndm3.hrs 1 Ndm3.hrs 1 secOndifrit soc,ket B
.
1 4~.4 1.1 97.5 2 5 - 2 38.9 5.6 87.4 12.6 3 33.4 11.1 75.0 25.0
4 27.8 16.7 62~5 37.5 o ~ 24.5 20.0 55.0 ` 45.0 6 22.3 22.2 50.1 ~9.9 7 ; 20.0 24.5 45.0 55.0 .....
Conjointly with the introduction of the reac-tion gases, the water condenser was fed with water at ~14C and the brine condenser was fed with cooling brine at -15C.
The exi t gas wash bo-ttles contained water as the washing liquid.
After a short time, the temperature in the reaction tube had risen to 223C. During the further course of -the test, it was kept at -this value by feeding cooling fluid to the temperature con-trol coil~ The exit gas leaving the brine condenser had a temperature of ~10C. The test was continued for 3 hours and the exit gas composition of the washed exit gas was determined by gas chromatography after 1/3 of this time and after 2/3 of this time. A thermal conduct-ivity detector was used for the gases oxygen~ carbon monoxide, carbon dioxide and ethylene, while a flame ioniza--tion detector was used for all-the other gases indicated `below~ The average values from both analyses are shown in 3 Table II, later in--the text, for Examples 1 to 7, the pro-portion of noble gas brought in via the air used having Z~78V~2 already been deducted from the oxygen figure.
When the test period had e~pired, t~e supply of gas to the reaction tube was stopped and the catalyst was cooled by blowing with air (of about roomtem-pera~ure). The condensate formed by the water and brinecondensers was combined, weighed and also analyzed by gas chromatography, using a flame ionization detector. me ~alues determined for Examples 1 to 7 are listed in Table late.r in the text.
lC The-following figures were found for Examples 1 to 7: .
Molar ratio HCl: C2H4:C12:02 = 2:2. 05 1 o.86.
Average residence time of the gases in the reaction space:
40 seconds. Space-time yield in g of crude 1,2-dichloro-ethane x hours 1 x dm 3, relative to 3.86 dm3 of reac-tion space:
Exam-ple No. 1 2 3 L~ 5 6 7 ., _ Space-ti.me yield 48.7 L~ . 448.3 L~ .O 47.8L~7.6 47.
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~) O ~ V V ~ V ~ r~ ~ r~ V C ) ~za~80~2 _ 28 -Examples_8 to 11 The same apparatus and the same type and quantity of ca-talyst were used as in Examples 1 to 7, but with the difference that a gas inlet tube havlng a spherical end was mounted on the reaction tube in the socket (C) nearest to the second frit, so that, as already mentioned above, ~he sphere of the gas inlet tube was at a distance from the second frit amounting to 17% of the total length of the reaction space. The socket furthest from the second frit and the socket at a distance from the - second frit amounting to 5~% of the height of the reaction space were not used. They were closed with plugs. A mixture of 90 Ndm3 x hours 1 of air and 22 Ndm3 x hours 1 of chlorine was introduced through the bottom aperture of the reaction tube and en'ered the reaction space via the first frit.
Part of the ethylene was introduced via the second frit and 44 ~dm3 x hours~l of hydrogen chloride gas and the remainder of the ethylene were introduced via the tube having the spherical end. In the individual examples~ a total of 45 Ndm3 x hours 1 of ethylene was passed into the reaction tube in each case, in the following fractions, through the two inlet points (the second frit ~nd socke-t C):
Ex~ Ethylene via: % of the total quantity of ample second socket ethylene 25 No. frit C first fraction second fraction Ndm3 hrs-l Ndm3 hrs~l v a(remainder) via _ .
8~3.9 - 1.1 97.6 2.4 93~.7 11.3 74.9 25.1 30 10 22.5 22.5 50.0 50-Q
~1 20.~ 24.7 45.1 54.~
12(~7~302 The temperature in the reaction space was kept constant at 222C and the test period was 3 hours.
Otherwise, the further procedure was as described in Example 1.
The following figures were ~ound for Examples 8 to 11:
Molar ratio: C2~4 HCl C12 2 :1.9 Average residence time of the gases in the reaction space:
40 seconds. ~Space-time yield in g of crude 1,2-dichloro-ethane x hours~l x dm~3, relative to a reaction space o~
3.86 dm~:
Example No. 8 9 10 11 Space-time yield L~.7 48.5 48.4 48.6 .. . ..
For the analyses of crude 1,2-dichloroethane and exit gas, see Tables III and IV below.
In all the examples described (Nos. 1 to 11), the reaction was carried out under normal atmospheric pressure, g7.3 kPa.
- :3L2~7802 _ 30 _ TABLE III
Analysis b~ ~as chromato~ra~hy of the crude lq2-dichloroethane condensed ComponentsExample Example Example Example No.8 No.9 No.10 No.ll % by % by % by % by wei~ht wei~ht wei~ht wei~ht 1,2-dichloroethane98.327 98.264 98.258 98.207 Total of ~2H2~ C2~
10 and C2H6 4 0.002 0.001 0.001 0.002 Vinyl chloride ~ 0.003 0.003 0.002 0,003 C2H5C1 0.011 0.020 0.020 0.022 1,2-dichloroethylene (trans) 0.018 0.020 0.018 0.017 15 l,l-dichloroethane0.009 O.OOg 0.009 0.010 CC14 0,0~2 0.089 0.094 0.088 1,2~dichloroethylene ~cis) 0.084 0.088 0.095 0.099 CHC13 0.054 0.055 0.056 0.063 1,1,2-trichloro-ethylene 0.005 0.005 0.006 0.006 1,1,2-trichloroethane 0.709 0.729 0.749 0.766 2-chloroe-thanol 0.003 0.003 0.003 0.003 1,1,2,2-tetrachloro~
ethane 0.340 0.355 0.351 0.369 Chloral 0.350 0.354 -335 0.340 .
:~L2~'7802 31 - `
TABLE IV
Analysis by rras chromato raph~_of '~ LIGc~5 , washing out hydro~en chloride Components Example Example Example Example No.8 No~9 No.10 No.ll % by % by % by % b~r volume volume volume volume _ 2 ~ 1.50 1.50 1.40 1.50 ~0. . ~.50 ~.60 2.60 2.55 10 ~0~ 3.20 3.30 3.35 3.30 C2H4 0 54 0.48 0.44 0.48 Yinyl chloride 0.002 0.002 0.001 0.002 2 5 1 0.012 0.013 0.014 0.011 Low-b~ilers 0.008 0.007 0.009 0.~08 15 1,2-dichloroe-thane 2.~ 2.35 2.~5 2,40 High-boilers ~0.001 ~0.001 ~0.001 ~0~001 1,1,2--trichloroethane0.004 0.003 0.005 0.004 C12 in the exit gasnone none none none - ~12 in the water none none none none C12 in the crude 1,2-dichloroethane none none none none % conversion, relative to:
HCl 97 97 97 97 Examples 12 and 13 The apparatus used for these was constructed analogously to tha-t used in Examples 1 to 7, but with the difference t~at a vertical nickel tube o~ in-ternal diameter 50 mm was used as the reaction space; this was equipped similarly to the glass tube in the apparatus used for Examples 1 to 7) with the following differences: there were only three tempera-ture measuremen-t poin-ts, dis-tributed , ~Z~780~
uniformly over the jacket of the reaction tube ~ounting upwards, the first two frits were fitted as described in the apparatus for Examples 1 to 7. There was then a third frit and beyond that a fourth. The distance from the second frit was 41% of the total internal length of the reaction space in the case of the third frit and was 47%
in the case of the fourth frit. At the top of the tube, immedia-tely before the narrowing, a fifth frit was also installed,whichwas used to reduce the pressure and to hold back entrained catalyst particles; the sphere envisaged for this purpose in the glass apparatus was omitted. A
pressure-reducing valve was fit-ted at the reactor outlet.
The gas inlet tube having a spherical head was fixed firmly in -the reactor, the distance from the sphere to the second frit (from below) being 56% of the length of the ~hole reaction space, measured between the bot-tom frit and the top frit in the tube. A pressure-measuring device was fitted in the upper section of the tube The capacity o~ -the reaction space, less the volu~e of the internal fitments contained in it (temperature control coil, gas inlet tubes together with frit or spherical head and temperature sensor) was 1,500 cm3. Water and brine condensers and hydrogen chloride washers were attached at the r~eactor outlet, after the pressure-reducing valve, as described in Examples 1 to 7.
The nickel tube was charged with 1 dm3 (apparent voIume) of a catalyst which contained copper chloride on al~linw~ oxide and had a copper con-tent of 4.5% by weight, rela-ti~e to the catalyst. The catalyst contained no iron ` ~2~7~0 , ~ _ 33 and had the following sieve analysis:
Particles ~20 ~ 22% by weight Particles ~20 ~ but ~70 ~ 67% by weight Particles ~70 ~ 11% by weight The true volwne of the catalyst was determined to be 310 cm3 by the water displacement method, as described abo~e. The free space available for the gas reaction was 1,190 cm3 Initial1y, 60 Ndm~ x hours 1 of air were blown 10 under pressure through the lowest gas inlet, through the first ~lowest) frit and the reac-tor was heated to 240C
by means of the temperature control coil. The pressure in the reactor was adjusted to 500 kPa by regulating the pressure-reducing valve at the top of the reactor. A con-stan-t temperature and pressure in the reaction tube were achieved after half an hour The rate at which air was blown in was then increased to 90 Ndm3 x hours 1 and gas was blown in at the following ra-tes through the second, third and fourth frits:
Ex- via 2nd frit via 3rd frit via 4-th frit % of the total NmOple Ndm3~hrs 1 Ndm3 hrs 1 Ndm3.hrs 1 qu nt ty of 2 4 + 2 4 C12 first second fraction fraction via 2nd via 3rd _ ~rit rit _ 13 50 13 _ 25 74~5 25.5 The temperature in the reaction space rose and was adjusted, by introducing a cooling medium into the tempera-ture control coil, to 280C in Example 12 and to 265C in Example 13, and was kept constant for a fur-ther 3 hours.
lZ(:~7802` i-The gases introduced into the reaction s~ace were pre-heated to 60C. After the expiry of 3 hours, the supply of gas was discontinued and the catalyst in the reaction tube was cooled by blowing with air (o~ about room ~em-perature).
During the whole test period, ~ater at ~12C was passed through the water condenser.and cooling brine at -20C was passed through the brine condenser.
The exit gas leaving the brine condenser had a tempera-ture of ~ C.
Samples were taken and evaluated as described under Examples 1 to 7 during and after each test, The figures obtained are listed in Tables V and VI which follow:
The follo~Yîng figures were found~for Examples 12 and 13:
Molar ratio: HCl:C2H4 (total):C12:02 2:2.04:1:0.75 A~erage residence time of the gases in the reaction space:
Example 12: 55 seconds; Example 13: 58 seconds.
Space~time yield in g of crude 1,2~dichloroethane x hours~l x dm 3, relative to a reaction space of 1.19 dm3:
Example 12: 181; Example 13: 182, ~2~780;~
TABLE V
AnalysLs by ~as chromato~raphy of the crude 1~2-dichloroethane condensed Components Example Example No.12 No.13 % by % by weight weight ~ . ._ 1,2-dichloroethane 97,083 97,779 Total of C2H2, C2H~ and C2H6 0.001 0,001 Vinyl chloride O.p28 0.022 C2H5Cl 0.068 0.06 1,2-dichloroethylene (trans) . 0.016 0.011 l,l-dichloroethane 0.006 0.006 CC14 0.048 0.054 1,2-dichloroethylene ~cis)0.042 0.038 C~C~3 0.0~5 0.017 1,1,2-trichloroet:hylene 0.00~ 0.005 1,1,2-trichloroethane 1.567 1,012 2-chloroethanol 0.033 0.042 1,1~2,2-tetrachloroethane 0,756 0.643 Chloral 0,310 0,290 1;~07t3 TABLE VI
Analysis ~ ~,as c'nromato~raph~ of the exit ~as after washin~_out hydro~en chloride Components Example Example No.12 No.l~
- % by % by volume volume 2 1.0 2.4 ~o 2.7 2.1 10 C02 3.1 2.8 C2H4 0.12 0.18 Vinyl chloride 0.040 0,025 C2H5Cl O.056 0,048 ~ow-boilers ~,o35 0,0~6 1,2-dichloroethane 2.65 2.25 High-boilers 0.01 0,005 1,1,2-trichloroethane 0.005 0,004 C12 in the exit gas none none C12 in the water none none C12 in the crude 1,2-dichloro-ethane none none Q,6 conversion~ relative to:
HCl 99 99 .C12 100 100 2 4 95.3 96.4 .
Conjointly with the introduction of the reac-tion gases, the water condenser was fed with water at ~14C and the brine condenser was fed with cooling brine at -15C.
The exi t gas wash bo-ttles contained water as the washing liquid.
After a short time, the temperature in the reaction tube had risen to 223C. During the further course of -the test, it was kept at -this value by feeding cooling fluid to the temperature con-trol coil~ The exit gas leaving the brine condenser had a temperature of ~10C. The test was continued for 3 hours and the exit gas composition of the washed exit gas was determined by gas chromatography after 1/3 of this time and after 2/3 of this time. A thermal conduct-ivity detector was used for the gases oxygen~ carbon monoxide, carbon dioxide and ethylene, while a flame ioniza--tion detector was used for all-the other gases indicated `below~ The average values from both analyses are shown in 3 Table II, later in--the text, for Examples 1 to 7, the pro-portion of noble gas brought in via the air used having Z~78V~2 already been deducted from the oxygen figure.
When the test period had e~pired, t~e supply of gas to the reaction tube was stopped and the catalyst was cooled by blowing with air (of about roomtem-pera~ure). The condensate formed by the water and brinecondensers was combined, weighed and also analyzed by gas chromatography, using a flame ionization detector. me ~alues determined for Examples 1 to 7 are listed in Table late.r in the text.
lC The-following figures were found for Examples 1 to 7: .
Molar ratio HCl: C2H4:C12:02 = 2:2. 05 1 o.86.
Average residence time of the gases in the reaction space:
40 seconds. Space-time yield in g of crude 1,2-dichloro-ethane x hours 1 x dm 3, relative to 3.86 dm3 of reac-tion space:
Exam-ple No. 1 2 3 L~ 5 6 7 ., _ Space-ti.me yield 48.7 L~ . 448.3 L~ .O 47.8L~7.6 47.
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. ~ .~ ~ ~ ~ O O O O C~l O O ~ ~ ~
~ t~ ;O r~l ~ O O O LO ~ O
~ Z ~ O L~ r~ O O O C~J O O ~ O
~t r~l ~t Q) ~ C\J Cs~ ~ ~
O 0 0 0 ~ O O O O Q) Q) Q>
O ~ O O O ~ O O ~ ~ ~
~: w O ~ r~l ; O O O ~ O
a~ r-l H ~
H 4~ 0 (~ r~ a) ~ J ao r~ 00 1~1 ~ ~ lt~ O L~ O O r~OLf\ O O O
~1 u2 ~ ~ C~ t~ O O O O 1~ 0 0 O r~ O O O ~ ~D O
~lt X Z ~ O L~ r~ H H0 0 0~1 0 O S~ O
rl X a) ~1) ~r~ ~ ~ O L~ L~ L~ O r~ H O O O 0 0 0 Q) ~ ~ ~ o o o c~.l o o ~
~ ~ O r~ O O O
+~ X ~; ~ O ~ r-l r-l OO O O ~I O O r~ O
o a;~ ~ o ,,. ,~ O
h r-l . .
. ~ a - ~ ~ h o ` ' ,s:: o ~ 0 ~ h a) ~ h ~
q~ ~ X ~ h. `
Ul f;o h 5~ h ~ a~ ~ a) a~
r-l ~ h O ~ O +~ ) r~
s~ O ~ C ) C\J r~
O ~I V ,D ~ I C~ ~ V C ) ~ i~ Q
Ei (~ ~ C\l b0 r~ ~\1 C~l ~ O
O (~1 0 0 C\J ~1 (\1 0 ~ . I H r~
~) O ~ V V ~ V ~ r~ ~ r~ V C ) ~za~80~2 _ 28 -Examples_8 to 11 The same apparatus and the same type and quantity of ca-talyst were used as in Examples 1 to 7, but with the difference that a gas inlet tube havlng a spherical end was mounted on the reaction tube in the socket (C) nearest to the second frit, so that, as already mentioned above, ~he sphere of the gas inlet tube was at a distance from the second frit amounting to 17% of the total length of the reaction space. The socket furthest from the second frit and the socket at a distance from the - second frit amounting to 5~% of the height of the reaction space were not used. They were closed with plugs. A mixture of 90 Ndm3 x hours 1 of air and 22 Ndm3 x hours 1 of chlorine was introduced through the bottom aperture of the reaction tube and en'ered the reaction space via the first frit.
Part of the ethylene was introduced via the second frit and 44 ~dm3 x hours~l of hydrogen chloride gas and the remainder of the ethylene were introduced via the tube having the spherical end. In the individual examples~ a total of 45 Ndm3 x hours 1 of ethylene was passed into the reaction tube in each case, in the following fractions, through the two inlet points (the second frit ~nd socke-t C):
Ex~ Ethylene via: % of the total quantity of ample second socket ethylene 25 No. frit C first fraction second fraction Ndm3 hrs-l Ndm3 hrs~l v a(remainder) via _ .
8~3.9 - 1.1 97.6 2.4 93~.7 11.3 74.9 25.1 30 10 22.5 22.5 50.0 50-Q
~1 20.~ 24.7 45.1 54.~
12(~7~302 The temperature in the reaction space was kept constant at 222C and the test period was 3 hours.
Otherwise, the further procedure was as described in Example 1.
The following figures were ~ound for Examples 8 to 11:
Molar ratio: C2~4 HCl C12 2 :1.9 Average residence time of the gases in the reaction space:
40 seconds. ~Space-time yield in g of crude 1,2-dichloro-ethane x hours~l x dm~3, relative to a reaction space o~
3.86 dm~:
Example No. 8 9 10 11 Space-time yield L~.7 48.5 48.4 48.6 .. . ..
For the analyses of crude 1,2-dichloroethane and exit gas, see Tables III and IV below.
In all the examples described (Nos. 1 to 11), the reaction was carried out under normal atmospheric pressure, g7.3 kPa.
- :3L2~7802 _ 30 _ TABLE III
Analysis b~ ~as chromato~ra~hy of the crude lq2-dichloroethane condensed ComponentsExample Example Example Example No.8 No.9 No.10 No.ll % by % by % by % by wei~ht wei~ht wei~ht wei~ht 1,2-dichloroethane98.327 98.264 98.258 98.207 Total of ~2H2~ C2~
10 and C2H6 4 0.002 0.001 0.001 0.002 Vinyl chloride ~ 0.003 0.003 0.002 0,003 C2H5C1 0.011 0.020 0.020 0.022 1,2-dichloroethylene (trans) 0.018 0.020 0.018 0.017 15 l,l-dichloroethane0.009 O.OOg 0.009 0.010 CC14 0,0~2 0.089 0.094 0.088 1,2~dichloroethylene ~cis) 0.084 0.088 0.095 0.099 CHC13 0.054 0.055 0.056 0.063 1,1,2-trichloro-ethylene 0.005 0.005 0.006 0.006 1,1,2-trichloroethane 0.709 0.729 0.749 0.766 2-chloroe-thanol 0.003 0.003 0.003 0.003 1,1,2,2-tetrachloro~
ethane 0.340 0.355 0.351 0.369 Chloral 0.350 0.354 -335 0.340 .
:~L2~'7802 31 - `
TABLE IV
Analysis by rras chromato raph~_of '~ LIGc~5 , washing out hydro~en chloride Components Example Example Example Example No.8 No~9 No.10 No.ll % by % by % by % b~r volume volume volume volume _ 2 ~ 1.50 1.50 1.40 1.50 ~0. . ~.50 ~.60 2.60 2.55 10 ~0~ 3.20 3.30 3.35 3.30 C2H4 0 54 0.48 0.44 0.48 Yinyl chloride 0.002 0.002 0.001 0.002 2 5 1 0.012 0.013 0.014 0.011 Low-b~ilers 0.008 0.007 0.009 0.~08 15 1,2-dichloroe-thane 2.~ 2.35 2.~5 2,40 High-boilers ~0.001 ~0.001 ~0.001 ~0~001 1,1,2--trichloroethane0.004 0.003 0.005 0.004 C12 in the exit gasnone none none none - ~12 in the water none none none none C12 in the crude 1,2-dichloroethane none none none none % conversion, relative to:
HCl 97 97 97 97 Examples 12 and 13 The apparatus used for these was constructed analogously to tha-t used in Examples 1 to 7, but with the difference t~at a vertical nickel tube o~ in-ternal diameter 50 mm was used as the reaction space; this was equipped similarly to the glass tube in the apparatus used for Examples 1 to 7) with the following differences: there were only three tempera-ture measuremen-t poin-ts, dis-tributed , ~Z~780~
uniformly over the jacket of the reaction tube ~ounting upwards, the first two frits were fitted as described in the apparatus for Examples 1 to 7. There was then a third frit and beyond that a fourth. The distance from the second frit was 41% of the total internal length of the reaction space in the case of the third frit and was 47%
in the case of the fourth frit. At the top of the tube, immedia-tely before the narrowing, a fifth frit was also installed,whichwas used to reduce the pressure and to hold back entrained catalyst particles; the sphere envisaged for this purpose in the glass apparatus was omitted. A
pressure-reducing valve was fit-ted at the reactor outlet.
The gas inlet tube having a spherical head was fixed firmly in -the reactor, the distance from the sphere to the second frit (from below) being 56% of the length of the ~hole reaction space, measured between the bot-tom frit and the top frit in the tube. A pressure-measuring device was fitted in the upper section of the tube The capacity o~ -the reaction space, less the volu~e of the internal fitments contained in it (temperature control coil, gas inlet tubes together with frit or spherical head and temperature sensor) was 1,500 cm3. Water and brine condensers and hydrogen chloride washers were attached at the r~eactor outlet, after the pressure-reducing valve, as described in Examples 1 to 7.
The nickel tube was charged with 1 dm3 (apparent voIume) of a catalyst which contained copper chloride on al~linw~ oxide and had a copper con-tent of 4.5% by weight, rela-ti~e to the catalyst. The catalyst contained no iron ` ~2~7~0 , ~ _ 33 and had the following sieve analysis:
Particles ~20 ~ 22% by weight Particles ~20 ~ but ~70 ~ 67% by weight Particles ~70 ~ 11% by weight The true volwne of the catalyst was determined to be 310 cm3 by the water displacement method, as described abo~e. The free space available for the gas reaction was 1,190 cm3 Initial1y, 60 Ndm~ x hours 1 of air were blown 10 under pressure through the lowest gas inlet, through the first ~lowest) frit and the reac-tor was heated to 240C
by means of the temperature control coil. The pressure in the reactor was adjusted to 500 kPa by regulating the pressure-reducing valve at the top of the reactor. A con-stan-t temperature and pressure in the reaction tube were achieved after half an hour The rate at which air was blown in was then increased to 90 Ndm3 x hours 1 and gas was blown in at the following ra-tes through the second, third and fourth frits:
Ex- via 2nd frit via 3rd frit via 4-th frit % of the total NmOple Ndm3~hrs 1 Ndm3 hrs 1 Ndm3.hrs 1 qu nt ty of 2 4 + 2 4 C12 first second fraction fraction via 2nd via 3rd _ ~rit rit _ 13 50 13 _ 25 74~5 25.5 The temperature in the reaction space rose and was adjusted, by introducing a cooling medium into the tempera-ture control coil, to 280C in Example 12 and to 265C in Example 13, and was kept constant for a fur-ther 3 hours.
lZ(:~7802` i-The gases introduced into the reaction s~ace were pre-heated to 60C. After the expiry of 3 hours, the supply of gas was discontinued and the catalyst in the reaction tube was cooled by blowing with air (o~ about room ~em-perature).
During the whole test period, ~ater at ~12C was passed through the water condenser.and cooling brine at -20C was passed through the brine condenser.
The exit gas leaving the brine condenser had a tempera-ture of ~ C.
Samples were taken and evaluated as described under Examples 1 to 7 during and after each test, The figures obtained are listed in Tables V and VI which follow:
The follo~Yîng figures were found~for Examples 12 and 13:
Molar ratio: HCl:C2H4 (total):C12:02 2:2.04:1:0.75 A~erage residence time of the gases in the reaction space:
Example 12: 55 seconds; Example 13: 58 seconds.
Space~time yield in g of crude 1,2~dichloroethane x hours~l x dm 3, relative to a reaction space of 1.19 dm3:
Example 12: 181; Example 13: 182, ~2~780;~
TABLE V
AnalysLs by ~as chromato~raphy of the crude 1~2-dichloroethane condensed Components Example Example No.12 No.13 % by % by weight weight ~ . ._ 1,2-dichloroethane 97,083 97,779 Total of C2H2, C2H~ and C2H6 0.001 0,001 Vinyl chloride O.p28 0.022 C2H5Cl 0.068 0.06 1,2-dichloroethylene (trans) . 0.016 0.011 l,l-dichloroethane 0.006 0.006 CC14 0.048 0.054 1,2-dichloroethylene ~cis)0.042 0.038 C~C~3 0.0~5 0.017 1,1,2-trichloroet:hylene 0.00~ 0.005 1,1,2-trichloroethane 1.567 1,012 2-chloroethanol 0.033 0.042 1,1~2,2-tetrachloroethane 0,756 0.643 Chloral 0,310 0,290 1;~07t3 TABLE VI
Analysis ~ ~,as c'nromato~raph~ of the exit ~as after washin~_out hydro~en chloride Components Example Example No.12 No.l~
- % by % by volume volume 2 1.0 2.4 ~o 2.7 2.1 10 C02 3.1 2.8 C2H4 0.12 0.18 Vinyl chloride 0.040 0,025 C2H5Cl O.056 0,048 ~ow-boilers ~,o35 0,0~6 1,2-dichloroethane 2.65 2.25 High-boilers 0.01 0,005 1,1,2-trichloroethane 0.005 0,004 C12 in the exit gas none none C12 in the water none none C12 in the crude 1,2-dichloro-ethane none none Q,6 conversion~ relative to:
HCl 99 99 .C12 100 100 2 4 95.3 96.4 .
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of 1,2-dichloro-ethane from ethylene by reaction with hydrogen chloride and inert gases containing oxygen, at 180 to 300°C and a pressure of 0.1 to 1.1 MPa, and by reaction with chlorine in the gas phase in the presence of a solid catalyst con-taining copper salts or copper and iron salts, with sub-sequent cooling and separation by distillation of the reaction mixture, both chlorination reactions being carried out successively in a common reaction space containing fluidized catalyst particles, and the heat formed in the whole reaction space being removed by indirect cooling with a liquid and/or gaseous heat transfer medium, which com-prises introducing, into the zone of the reaction space in which the first chlorination reaction takes place, 98 to 40% of the total quantity of the volume of ethylene intro-duced into the common reaction space, and introducing, into the zone of the reaction space in which the second chlorina-tion reaction takes place, the remaining 2 to 60% of the total quantity of the volume of ethylene introduced into the common reaction space.
2. The process as claimed in claim 1, wherein 95 to 60%
of the total quantity of the volume of ethylene introduced into the common reaction space is introduced into the zone of the react on space in which the initial chlorination reaction takes place, and the remaining 5 to 40% of the total quantity of the volume of ethylene introduced into the common reaction space is introduced into the zone of the reaction space in which the second chlorination takes place.
of the total quantity of the volume of ethylene introduced into the common reaction space is introduced into the zone of the react on space in which the initial chlorination reaction takes place, and the remaining 5 to 40% of the total quantity of the volume of ethylene introduced into the common reaction space is introduced into the zone of the reaction space in which the second chlorination takes place.
3. The process as claimed in claim 1 or 2, wherein the gases to be reacted flow continuously through the reaction space, hydrogen chloride, a fraction of the ethylene, and inert gas containing oxygen being introduced, separately, or in part separately, from one another into an initially-situated zone of the reaction space, in the direction of flow of the gases, and the residual fraction of the ethylene, and chlorine being introduced, separately from one another, into a subsequent zone of the reaction space, in the direction of flow, in the following ratios:
2 moles of HCl, 1.8 to 2.2. moles, total quantity, of C2H4, 0.5 to 0.6 mole of O2 and 0.79 to 1.2 moles of Cl2, the quantity of chlorine being such that less than 0.001% by weight of free, elementary chlorine is found in the gas mixture leaving the reaction space.
2 moles of HCl, 1.8 to 2.2. moles, total quantity, of C2H4, 0.5 to 0.6 mole of O2 and 0.79 to 1.2 moles of Cl2, the quantity of chlorine being such that less than 0.001% by weight of free, elementary chlorine is found in the gas mixture leaving the reaction space.
4. The process as claimed in claims 1 or 2, wherein the gases to be reacted flow continuously through the reaction space, inert gas containing oxygen, and chlorine and also, separately therefrom, a fraction of the ethylene being introduced into an initially-situated zone of the reaction space, in the direction of flow of the gases, and hydrogen chloride and the remaining fraction of the ethylene being introduced into a subsequent zone of the reaction space, in the direction of flow, in the following ratios: 2 moles, total quantity, of C2H4, 0.9 to 1.2 moles of Cl2, 1.6 to 2.3 moles of HCl and 0.35 to 1.3 moles of O2, the quantity of oxygen or hydrogen chloride being such that less than 0.001% by weight of free, elementary chlorine is found in the gas mixture leaving the reaction space.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813106983 DE3106983A1 (en) | 1981-02-25 | 1981-02-25 | "METHOD FOR PRODUCING 1,2-DICHLORETHANE" |
| DEP3106983.5 | 1981-02-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1207802A true CA1207802A (en) | 1986-07-15 |
Family
ID=6125680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000396999A Expired CA1207802A (en) | 1981-02-25 | 1982-02-24 | Process for the manufacture of 1,2-dichloroethane |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0058976B1 (en) |
| JP (1) | JPS57156424A (en) |
| AR (1) | AR228084A1 (en) |
| BR (1) | BR8200922A (en) |
| CA (1) | CA1207802A (en) |
| CS (1) | CS228538B2 (en) |
| DD (1) | DD201582A5 (en) |
| DE (2) | DE3106983A1 (en) |
| ES (1) | ES509720A0 (en) |
| HU (1) | HU191344B (en) |
| MX (1) | MX156086A (en) |
| NO (1) | NO820572L (en) |
| SU (1) | SU1240349A3 (en) |
| ZA (1) | ZA821204B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0113513B1 (en) * | 1982-12-24 | 1986-03-12 | Imperial Chemical Industries Plc | Production of 1,2-dichloroethane |
| DE3837668A1 (en) * | 1988-11-05 | 1990-05-10 | Hoechst Ag | Process for the preparation of 1,2-dichloroethane |
| WO2023141486A1 (en) * | 2022-01-19 | 2023-07-27 | Oxy Vinyls, Lp | Oxychlorination process |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4172099A (en) * | 1972-05-30 | 1979-10-23 | Stauffer Chemical Company | Process for chlorination of ethylene |
| FR2211427B1 (en) * | 1972-12-27 | 1976-10-29 | Rhone Progil | |
| JPS50105604A (en) * | 1974-01-25 | 1975-08-20 | ||
| JPS50105603A (en) * | 1974-01-25 | 1975-08-20 | ||
| DE2922375A1 (en) * | 1979-06-01 | 1980-12-11 | Hoechst Ag | METHOD FOR PRODUCING 1,2-DICHLORETHANE |
-
1981
- 1981-02-25 DE DE19813106983 patent/DE3106983A1/en not_active Withdrawn
-
1982
- 1982-02-18 ES ES509720A patent/ES509720A0/en active Granted
- 1982-02-19 BR BR8200922A patent/BR8200922A/en unknown
- 1982-02-20 EP EP82101317A patent/EP0058976B1/en not_active Expired
- 1982-02-20 DE DE8282101317T patent/DE3262843D1/en not_active Expired
- 1982-02-23 DD DD82237627A patent/DD201582A5/en not_active IP Right Cessation
- 1982-02-23 AR AR288526A patent/AR228084A1/en active
- 1982-02-24 ZA ZA821204A patent/ZA821204B/en unknown
- 1982-02-24 CS CS821271A patent/CS228538B2/en unknown
- 1982-02-24 HU HU82558A patent/HU191344B/en not_active IP Right Cessation
- 1982-02-24 JP JP57027567A patent/JPS57156424A/en active Granted
- 1982-02-24 NO NO820572A patent/NO820572L/en unknown
- 1982-02-24 CA CA000396999A patent/CA1207802A/en not_active Expired
- 1982-02-24 SU SU823394505A patent/SU1240349A3/en active
- 1982-02-25 MX MX191560A patent/MX156086A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA821204B (en) | 1983-01-26 |
| DE3262843D1 (en) | 1985-05-09 |
| ES8301861A1 (en) | 1983-01-16 |
| DE3106983A1 (en) | 1982-09-09 |
| MX156086A (en) | 1988-07-01 |
| SU1240349A3 (en) | 1986-06-23 |
| ES509720A0 (en) | 1983-01-16 |
| EP0058976A1 (en) | 1982-09-01 |
| JPH0244287B2 (en) | 1990-10-03 |
| HU191344B (en) | 1987-02-27 |
| AR228084A1 (en) | 1983-01-14 |
| EP0058976B1 (en) | 1985-04-03 |
| JPS57156424A (en) | 1982-09-27 |
| BR8200922A (en) | 1982-12-28 |
| NO820572L (en) | 1982-08-26 |
| DD201582A5 (en) | 1983-07-27 |
| CS228538B2 (en) | 1984-05-14 |
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