CA1089879A - Oxychlorination of ethylene - Google Patents
Oxychlorination of ethyleneInfo
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- CA1089879A CA1089879A CA339,794A CA339794A CA1089879A CA 1089879 A CA1089879 A CA 1089879A CA 339794 A CA339794 A CA 339794A CA 1089879 A CA1089879 A CA 1089879A
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Abstract
OXYCHLORINATION OF ETHYLENE
Abstract of the Disclosure Oxychlorination of ethylene is carried out using a three-reactor system containing beds of a catalyst comprising a spherical, high-surface area activated alumina impregnated with cupric chloride and potassium chloride. In the first two reactors, the catalyst bed is divided into two sections, with a more active catalyst in the lower section than in the upper. The catalyst is substantially undiluted with inert particles.
Abstract of the Disclosure Oxychlorination of ethylene is carried out using a three-reactor system containing beds of a catalyst comprising a spherical, high-surface area activated alumina impregnated with cupric chloride and potassium chloride. In the first two reactors, the catalyst bed is divided into two sections, with a more active catalyst in the lower section than in the upper. The catalyst is substantially undiluted with inert particles.
Description
Background and Prior Art This invention relates to the oxychlorination of ethylene in a fixed bed catalytic process to produce chlorinated hydrocar~ons, particularly 1,2-dichloroethane.
It is well known that hydrocarbons such as ethylene may be chlorinated by reacting them with hydrogen chloride and gases containing elemental oxygen, particularly air, in the presence of a catalyst at elevated temperatures and pressures. Such a process is generally termed an "oxy-; 10 chlorination" or a Deacon process and usually employs a catalyst comprising a chloride of a metal having at least two valences, generally on a porous refractory support.
The most common catalyst for such processes comprises cupric chloride on a particulate material such as activated alumina, silica, alumina-silica, diatomaceous earth, etc. Activated alumina, in one or another of its various forms, isthe most common support utilized. In addition, the catalyst may contain additives such as alkali metal chlorides, rare earth metal chlorides, and other metallic compounds which assist in promoting the desired reaction and/or inhibiting the progress of side reactions. Particu-larly, potassium chloride has been utilized as an additive to such a catalyst when it is desired to produce 1,2-dichloroethane from ethylene since potassium chloride is known to s~ppress the formation of ethyl chloride. The ; amount of potassium chloride used, however, is kept low as it also tends to decrease the activity of the catalyst towards the primary reaction.
In the conduct of such a fixed bed oxychlorination process one of the concerns is the control of the reaction temperature. The oxychlorination reaction itself is highly :
exothermic and, in addition, control of the reaction temper-ature is hampered by the fact that the catalyst bed itself has a low heat conductivity. As a result of these two factors, there is a danger of the formation of undesirably extra-ordinarily high localized temperature zones in the catalyst bed. Numerous expedients have been proposed in the art aimed at preventing or at least minimizing the existence of such exceptionally high localized temperatures. For example, it has been variously proposed to control temperature by adjusting the ratio of the reactants; by diluting the feed ;
with an inert gas or an excess of one or more reactant gases; by utilizing a tubular reactor with controlled external cooling and/or tubes of varying diameters; by -diluting the catalyst particles with inert particles; and by varying the particle size of the catalyst and/or inert particles. ~,, Particularly when the reaction is conducted in tubular reactors, it is known in the art, for example as described in U.S. Patent 3,184,515, that the problem of undesirably high localized temPeratures does not exist through-out the entire reactor. This is a result of the nature of the oxychlorination reaction itself, which becomes progressive-ly less vigorous in the direction of flow of the reaction mixture. At the inlet of the,catalyst bed, the reaction proceeds rapidly and strongly and control of both the temperature and location of the hot spot (point o~ highest temperature) in the bed is important. ~owever, as the reactants proceed through the bed, the reaction becomes somewhat less vigorous as oxygen is consumed. This is particularly the case when, as is known in the art, the oxychlorination process is carried out in a series of two or more catalytic reactors with the total air (or oxygen) feed being split between the several reactors. Thus, as the oxychlorination feed mixture reacts, oxygen is used up toward the outlet of each reactor and the concern of a runaway reaction or overly high localized temperature in this zone is less than in the portion of the reactor closer to the inlet.
One solution which has been proposed for accomplish-ing acceptable conversions and selectivity to dichloro-ethane as well as obtaining reasonable control of the reaction temperatures and formation of high localized temperatures is to dilute the catalyst with inert particles intermingled with the catalyst particles. The inert particles may consist of, for example, silica, alumina, graphite, glass beads, etc. In some processes, the pro-portions of catalyst to diluent in the oxychlorination reactor have been varied. At the inlet side of the reactor, it is desirable to have a less concentrated catalyst because of the danger of runaway reactions or high localized temper-atures. However, further from the inlet, as the reaction proceeds and becomes less vigorous, these dangers are not quite so prominent and in fact, it would be desirable to have a more highly active catalyst to continue promoting the reaction as oxygen is consumed. ~hus, it is common when using diluted catalysts to divide the bed into two or more zones, each zone containing a different ratio of catalyst to diluent, with the ratio of catalyst to diluent increasing toward the outlet end of the reactor. For example, in U.S. Patent 3,184,515, a process is described (Example 1) 3Q using a diluted catalyst in which the reaction tube is divided into four zones, the first zone containing 7 volume percent ~Q89879 catalyst anà 93 volume percent graphite diluent, the second zone containing catalyst to diluent in a 15:85 volume percent ratio, the third containing a 40:60 mixture, and the fourth containing 100 percent catalyst. In another variation, a fairly highly active catalyst may be placed at the very --inlet of the reactor in order to initiate the reaction, immediately followed by a much less active catalyst to prevent the formation of hot spots in the adjacent reaction zone.
The use of a diluted catalyst such as described in the preceding paragraphs, however, possesses several dis-advantages. In the first place, it requires loading of the catalyst in several different reaction zones and thus, the formati~n of several catalyst-diluent mixtures of different proportions. Of greater concern however, is the fact that the mixing of catalyst and diluent can result in a non-uniform mixture There is, therefore, a likelihood of formation of undesirably high localized temperatures due to a concentration of catalyst particles in a particular section of the reaction zone if the mixing is not carried out to a sufficiently thorough degree. Additionally, in many cases the diluent particles are not of the same general size or shape as the catalyst particles. It has been proposed, for instance, to dilute cylindrical catalyst particles or spherical catalyst particles with diluent particles of a different shape or size.
In such cases, the overall mixture does not provide a rea-sonably uniform surface to the reactants and the pressures -and/or pressure drops occurring during the reaction may be other than advantageous. Even if the diluent particles possess the same relative shape or size as the catalyst 3~ particles, there is still the li~elihood that the diluent and catalyst will not be satisfactorily mixed and hot spots lQ89879 can result, as well as the nuisance of having to mix up different catalyst-diluent mixtures for the different reaction zones.
Another solution which has been proposed has been to provide a catalyst, either with or without diluent particles, in which the particle size decreases from inlet to outlet. Such a concept is described in U.S. Patent 3,699,178. However, such a practice, even if the catalyst is utilized without a diluent, re~uires careful manufacture to assure that the particle sizes are as desired and requires the manufacture of at least two, and very likely three or four different catalysts, in order to attain the objectives of this concept. In the alternative embodiment of this concept, in which the catalyst is intermingled with diluent particles, the disadvantages of utilizing diluent particles are added to those involving the preparation of different sized catalyst particles.
It is an object of the present invention to pro-vide an oxychlorination process for the production of 1,2-dichloroethane from ethylene.
It is a further object of this invention to pro-vide an oxychlorination process for the production of l,2-dichloroethane from ethylene in which hot spot location and temperature can be readily controlled.
~t is another obiect of the present invention to provide a process for the production of 1,2-dichloroethane by oxychlorination of ethylene at high hydrogen chloride conversion rates.
Another object of the present invention is to pro~ide such a process in which a substantially uniform pressure drop can be maintained for a reasonably long period of time.
Yet another object of the present invention is to provide such a process in which selectivity of conversion of ethylene to 1,2-dichloroethane is acceptably high, and in which excesses of reactants such as ethylene and/or air can be kept to a minimum.
Still another object of the present invention is to provide such a process which can be carried out at high flow rates of reactants.
Another object of *he present invention is to provide a system and process for the oxychlorination of ethylene which can be run using either air or oxygen as the oxygen-containing gas.
Yet another object of the present invention is to provide a new catalyst for use in conducting the oxy-chlorination of ethylene to 1,2-dichloroethane with the above advantages.
Summary of the Invention -In brief, the invention herein comprises the -providing of a novel oxychlorination process utilizing a novel catalyst comprising cupric chloride and potassium chloride supported on a spherically shaped activated alumina having a high surface area and a high structural integrity.
Ethylene is converted to 1,2-dichloroethane at high rates of conversion and selectivity with good hot spot control and very little increase in pressure drop over long periods of time by utilizing such a catalyst in a series of three reactors, in which the catalyst is utilized substantially without the presence of an inert diluent, the content and weight ratio of cupric and potassium chlorides in the catalyst being varied within each reactor. Tn each of the first two reactors, the catalyst bed is diveded into two zones, 10~9879 the catalyst in the zone nearest the inlet preferably having a somewhat lower content of cupric chloride and a higher weight ratio of potassium chloride to cupric chloride than the catalyst in the zone nearest the outlet.
In yet another aspect, this invention comprises a system for the carrying out of an oxychlorination process, comprising the aforesaid catalyst situated in reactors as herein described.
More particularly, in one aspect, the invention herein comprises a process for the oxychlorination of ethylene in a fixed bed comprising the steps of:
(a) reacting ethylene, hydrogen chloride and a first portion of an oxygen-containing gas in a first reaction zone in contact with a first catalyst bed substantially undiluted by catalytically inert particles and comprising cupric chloride and potassium chloride supported on spherical particles of activated alumina, the first catalyst bed being divided into two portions in the direction of flow of reactants therethrough, the first portion comprising between about 45~ and about 7S% of the bed, the second portion comprising between about 25% and about 55% of the bed, the first portion comprising between about 4.5 and about 12.5 weight % cu~ric chloride and between about l.S and about 7 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about l.S:l and about 4 1, the second portion comprising between about 12 and about 25 weight %
cupric chloride and between about 0.5 and about 4 weight %
pota~ssium chloride, in a weight ratio of cupric chloride to potassi~m chloride of between ahout 5:1 and about 15:1;
(b) reacting the products of step (a) and a second portion of an oxygen-containing gas in a second reaction zone in contact with a second catalyst bed sub-stantially undiluted by catalytically inert particles and comprising cupric chloride and potassium chloride supported on spherical particles of activated alumina, the second catalyst bed being divided into two portions in the direction of flow of reactants therethrough, the first portion comprising between about 45% and about 75% of the bed, the second portion comprising between a~out 25% and about 55%
of the bed, the first portion of the bed comprising between about 5.5 and about 15 weight % cupric chloride and between about l and about 5 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about 2:1 and about 6:1, the second portion of the bed com-prising between about 12 and about 25 weight % cupric chloride - --and between about 0.5 and about 4 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between 5:1 and about 15:1; and, (c) reacting the products of step (b) and a third portion of an oxyqen-containing gas in a third reaction zone in contact with a third catalyst bed substantially undiluted by catalytically inert particles and comprising between about 12 and about 25 weight % cupric chloride and about 0.5 and about 4 weight % potassium chloride, supported on spherical particles of activated alumina, in a weight ratio of cupric chloride to potassium chloride of between about 5:1 and about 15:1.
In another aspect, this in~ention comprises a catalyst comprising cupric chloride and potassium chloride supported on a base comprising spherical particles of activated alumina, said base having a BET surface area of ~Q89879 between about 225 and about 275 m2/g, an attrition hardr.~ss of at least 90%, a total nitrogen pore volume of between about 0.3 and about 0.6 cc/g, an average pore diameter of between about 50 and about lO0 A, between about 20 and about 50% of the pore volume composed of pores having a diameter of between about 80 and 600 A and further characterized by an X-ray diffraction pattern as hereinafter defined and sub-stantially no observable grain boundaries after etching with HF.
In a third aspect, this invention comprises a reaction system for oxychlorination of ethylene in the presence of a catalyst comprising cupric and potassium chlorides supported on spherical particles of activated alumina, the reaction system comprising:
(a) a first reaction zone comprising a first catalyst bed divided into two portions in the direction of f low of reactants therethrough, the first portion comprising between about 45% and about 75% of the bed, the second portion comprising between about 25~ and about 55% of the bed, the first portion comprising between about 4.5 and about 12.5 weight % cupric chloride and between about 1.5 and about 7 weight % potassium chloride in a weight ratio of cupric chloride to potassium chloride of between about 1.5:1 and about 4:1, the second portion comprising between a~out 12 and about 25 weight % cupric chloride and between about 0.5 and about 4 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about 5:1 and about 15:1;
(b) a second reaction zone comprising a second catalyst bed divided into two portions in the direction of flow of reactants therethrough, the first portion comprising lQ8g879 between about 45% and about 75% of the bed, the second portion comprising between about 25% and about 55% of the bed, the first portion comprising between about 5.5 and about 15 weight % cupric chloride and between about 1 and about 5 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about 2:1 and about 6:1, the second portion of the bed comprising between about 12 and about 25 weight % cupric chloride and between about 0.5 and about 4 weight % potassium chloride, in a - -.
weight ratio of cupric chloride to potassium chloride of between about S:l and about 15:1;
(c) a third reaction zone comprising a third catalyst bed comprising between about 12 and about 25 weight % cupric chloride and between about 0.5 and about 4 weight potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about S:l and about lS:l.
Detailed Description of the Invention The invention will be described with reference to the Figure, which depicts an illustrative flow sheet for carrying out the process and utilizing the catalyst and system of the present invention.
The catalyst is prepared by conventional impreg-nation techni~ues utilizing a~ueous solutions of cupric and potassium chlorides, as further described in the examples which follow. The support which is impregnated as a spherical particulate high surface area activated alumina, that is, an alumina havlng a BET surface area of at least 100 m /g, preferably between about 225 and about 275 m /g, and also an attrition hardness of at least 90%, a total nitrogen pore ~olume of between about 0.3 and about 0.6 cc/g, and an average pore diameter of between about 50 andabout 100 A, wherein between about 20 and about 50% of the pore volume is composed of pores ha~ing a diameter of between about 80 and about 600 A. The alumina is further characterized by an X-ray diffraction pattern having three main peaks: diffuse peaks at 1.39 and 1.98 A and another peak at 2.34 A, the ratio of intensity of the peak at 1.39 A to that at 1.98 A
being between about 1.5:1 to about 5:1, and by showing sub-stantially no observable grain boundaries after etching with HF. Supports having these properties have been found to have good structural integrity even over lengthy periods of operation. Examples of suitable supports of this type are aluminas currently available under the designations HSC-ll ~, from Houdry Process and Chemical Company and SCM-250~, from Rhone-Progil.
As seen in the Figure, the process is conducted in three reactors in series, designated Rl, R2 and R3. Each of the reactors contains a catalyst bed, 12, 14, and 16 re-spectively. The reactors are preferably tubular reactors, having tubes packed with the catalyst. In reactor Rl, the catalyst bed is divided into two parts in the direction of the flow of reactants therethrough. The first part, at the inlet side of the reactor, comprises between about 45 and about 75%, preferably between about 5~ and about 65~, of the length of the catalyst bed and contains a catalyst having between about 4.5 and about 12.5, preferably between about ~ and a~out 8, and most preferably between about 5.5 and about 6.5 weight % cupric chloride, and between about 1.5 and about 7, preferably between about 2 and about 4, and most preferably between about 2.7 and 3.3 weight % potassium chloride, wherein the weight ratio of cupric chloride to potassium chlorideis between about 1.5:1 and 4:1, preferably between about 1.5:1 and 3:1, and most preferably about 2:1.
The second half of the bed, at the outlet end of the reactor, comprises correspondingly between about 25 and about 55%, preferably between about 35 and about 45%, of the bed length and contains a catalyst having between about 12 and about 25 weight %, preferably between about 15 and about 20 weight %, cupric chloride, between about 0.5 and about 4 weight %, preferably between about 1.5 and about 3 weight ~, of potassium chloride, the weight ratio of cupric to potassium chlorides being between about 5:1 and about 15:1, preferably between about 5:1 and about 12:1, most preferably about 10:1. Thus, the catalyst bed 12 of reactor Rl contains two types of catalysts: a first catalyst in the section of the bed towards the inlet, having a relatively lower activity in order to ensure that the reaction does not become uncontrollable in its early stages, and a second catalyst having a higher cupric chloride content and therefore, a higher activity, in the portion of the reactor towards the outlet, to continue the reaction at the point at which the reaction begins to lose vigor due to the consumption of oxygen.
~eactor R2 contains catalyst bed 14 which is also divided into two portions. The first portion of the catalyst bed, at the inlet side of the reactor, comprises between about 45 and about 75%, preferably between about 55 and about 65%, o~ the bed length and the second portion, toward the outlet end, comprises between about 25 and about 55%, preferably between about 35 and about 45%, correspondingly, of the bed length. The catalyst in the first portion of the bed 14 in reactor R2 can be somewhat stronger or more active than the catalyst in the first portion of the bed 12 in reactor ~1 -since the reaction has already proceeded partway towards completion. In reactor R2, the catalyst in the first portion of the bed contains between about 5.5 and about 15%, pre-ferably between about 7.5 and about 12.5%, and most preferably between about 9 and about 11 weight % cupric chloride, and between about 1 and about 5, preferably between about 1.5 and about 3.5, and most preferably between about 2.5 and about 3.5 weight % potassium chloride, the weight ratio of cupric chloride to potassium chloride being between about
It is well known that hydrocarbons such as ethylene may be chlorinated by reacting them with hydrogen chloride and gases containing elemental oxygen, particularly air, in the presence of a catalyst at elevated temperatures and pressures. Such a process is generally termed an "oxy-; 10 chlorination" or a Deacon process and usually employs a catalyst comprising a chloride of a metal having at least two valences, generally on a porous refractory support.
The most common catalyst for such processes comprises cupric chloride on a particulate material such as activated alumina, silica, alumina-silica, diatomaceous earth, etc. Activated alumina, in one or another of its various forms, isthe most common support utilized. In addition, the catalyst may contain additives such as alkali metal chlorides, rare earth metal chlorides, and other metallic compounds which assist in promoting the desired reaction and/or inhibiting the progress of side reactions. Particu-larly, potassium chloride has been utilized as an additive to such a catalyst when it is desired to produce 1,2-dichloroethane from ethylene since potassium chloride is known to s~ppress the formation of ethyl chloride. The ; amount of potassium chloride used, however, is kept low as it also tends to decrease the activity of the catalyst towards the primary reaction.
In the conduct of such a fixed bed oxychlorination process one of the concerns is the control of the reaction temperature. The oxychlorination reaction itself is highly :
exothermic and, in addition, control of the reaction temper-ature is hampered by the fact that the catalyst bed itself has a low heat conductivity. As a result of these two factors, there is a danger of the formation of undesirably extra-ordinarily high localized temperature zones in the catalyst bed. Numerous expedients have been proposed in the art aimed at preventing or at least minimizing the existence of such exceptionally high localized temperatures. For example, it has been variously proposed to control temperature by adjusting the ratio of the reactants; by diluting the feed ;
with an inert gas or an excess of one or more reactant gases; by utilizing a tubular reactor with controlled external cooling and/or tubes of varying diameters; by -diluting the catalyst particles with inert particles; and by varying the particle size of the catalyst and/or inert particles. ~,, Particularly when the reaction is conducted in tubular reactors, it is known in the art, for example as described in U.S. Patent 3,184,515, that the problem of undesirably high localized temPeratures does not exist through-out the entire reactor. This is a result of the nature of the oxychlorination reaction itself, which becomes progressive-ly less vigorous in the direction of flow of the reaction mixture. At the inlet of the,catalyst bed, the reaction proceeds rapidly and strongly and control of both the temperature and location of the hot spot (point o~ highest temperature) in the bed is important. ~owever, as the reactants proceed through the bed, the reaction becomes somewhat less vigorous as oxygen is consumed. This is particularly the case when, as is known in the art, the oxychlorination process is carried out in a series of two or more catalytic reactors with the total air (or oxygen) feed being split between the several reactors. Thus, as the oxychlorination feed mixture reacts, oxygen is used up toward the outlet of each reactor and the concern of a runaway reaction or overly high localized temperature in this zone is less than in the portion of the reactor closer to the inlet.
One solution which has been proposed for accomplish-ing acceptable conversions and selectivity to dichloro-ethane as well as obtaining reasonable control of the reaction temperatures and formation of high localized temperatures is to dilute the catalyst with inert particles intermingled with the catalyst particles. The inert particles may consist of, for example, silica, alumina, graphite, glass beads, etc. In some processes, the pro-portions of catalyst to diluent in the oxychlorination reactor have been varied. At the inlet side of the reactor, it is desirable to have a less concentrated catalyst because of the danger of runaway reactions or high localized temper-atures. However, further from the inlet, as the reaction proceeds and becomes less vigorous, these dangers are not quite so prominent and in fact, it would be desirable to have a more highly active catalyst to continue promoting the reaction as oxygen is consumed. ~hus, it is common when using diluted catalysts to divide the bed into two or more zones, each zone containing a different ratio of catalyst to diluent, with the ratio of catalyst to diluent increasing toward the outlet end of the reactor. For example, in U.S. Patent 3,184,515, a process is described (Example 1) 3Q using a diluted catalyst in which the reaction tube is divided into four zones, the first zone containing 7 volume percent ~Q89879 catalyst anà 93 volume percent graphite diluent, the second zone containing catalyst to diluent in a 15:85 volume percent ratio, the third containing a 40:60 mixture, and the fourth containing 100 percent catalyst. In another variation, a fairly highly active catalyst may be placed at the very --inlet of the reactor in order to initiate the reaction, immediately followed by a much less active catalyst to prevent the formation of hot spots in the adjacent reaction zone.
The use of a diluted catalyst such as described in the preceding paragraphs, however, possesses several dis-advantages. In the first place, it requires loading of the catalyst in several different reaction zones and thus, the formati~n of several catalyst-diluent mixtures of different proportions. Of greater concern however, is the fact that the mixing of catalyst and diluent can result in a non-uniform mixture There is, therefore, a likelihood of formation of undesirably high localized temperatures due to a concentration of catalyst particles in a particular section of the reaction zone if the mixing is not carried out to a sufficiently thorough degree. Additionally, in many cases the diluent particles are not of the same general size or shape as the catalyst particles. It has been proposed, for instance, to dilute cylindrical catalyst particles or spherical catalyst particles with diluent particles of a different shape or size.
In such cases, the overall mixture does not provide a rea-sonably uniform surface to the reactants and the pressures -and/or pressure drops occurring during the reaction may be other than advantageous. Even if the diluent particles possess the same relative shape or size as the catalyst 3~ particles, there is still the li~elihood that the diluent and catalyst will not be satisfactorily mixed and hot spots lQ89879 can result, as well as the nuisance of having to mix up different catalyst-diluent mixtures for the different reaction zones.
Another solution which has been proposed has been to provide a catalyst, either with or without diluent particles, in which the particle size decreases from inlet to outlet. Such a concept is described in U.S. Patent 3,699,178. However, such a practice, even if the catalyst is utilized without a diluent, re~uires careful manufacture to assure that the particle sizes are as desired and requires the manufacture of at least two, and very likely three or four different catalysts, in order to attain the objectives of this concept. In the alternative embodiment of this concept, in which the catalyst is intermingled with diluent particles, the disadvantages of utilizing diluent particles are added to those involving the preparation of different sized catalyst particles.
It is an object of the present invention to pro-vide an oxychlorination process for the production of 1,2-dichloroethane from ethylene.
It is a further object of this invention to pro-vide an oxychlorination process for the production of l,2-dichloroethane from ethylene in which hot spot location and temperature can be readily controlled.
~t is another obiect of the present invention to provide a process for the production of 1,2-dichloroethane by oxychlorination of ethylene at high hydrogen chloride conversion rates.
Another object of the present invention is to pro~ide such a process in which a substantially uniform pressure drop can be maintained for a reasonably long period of time.
Yet another object of the present invention is to provide such a process in which selectivity of conversion of ethylene to 1,2-dichloroethane is acceptably high, and in which excesses of reactants such as ethylene and/or air can be kept to a minimum.
Still another object of the present invention is to provide such a process which can be carried out at high flow rates of reactants.
Another object of *he present invention is to provide a system and process for the oxychlorination of ethylene which can be run using either air or oxygen as the oxygen-containing gas.
Yet another object of the present invention is to provide a new catalyst for use in conducting the oxy-chlorination of ethylene to 1,2-dichloroethane with the above advantages.
Summary of the Invention -In brief, the invention herein comprises the -providing of a novel oxychlorination process utilizing a novel catalyst comprising cupric chloride and potassium chloride supported on a spherically shaped activated alumina having a high surface area and a high structural integrity.
Ethylene is converted to 1,2-dichloroethane at high rates of conversion and selectivity with good hot spot control and very little increase in pressure drop over long periods of time by utilizing such a catalyst in a series of three reactors, in which the catalyst is utilized substantially without the presence of an inert diluent, the content and weight ratio of cupric and potassium chlorides in the catalyst being varied within each reactor. Tn each of the first two reactors, the catalyst bed is diveded into two zones, 10~9879 the catalyst in the zone nearest the inlet preferably having a somewhat lower content of cupric chloride and a higher weight ratio of potassium chloride to cupric chloride than the catalyst in the zone nearest the outlet.
In yet another aspect, this invention comprises a system for the carrying out of an oxychlorination process, comprising the aforesaid catalyst situated in reactors as herein described.
More particularly, in one aspect, the invention herein comprises a process for the oxychlorination of ethylene in a fixed bed comprising the steps of:
(a) reacting ethylene, hydrogen chloride and a first portion of an oxygen-containing gas in a first reaction zone in contact with a first catalyst bed substantially undiluted by catalytically inert particles and comprising cupric chloride and potassium chloride supported on spherical particles of activated alumina, the first catalyst bed being divided into two portions in the direction of flow of reactants therethrough, the first portion comprising between about 45~ and about 7S% of the bed, the second portion comprising between about 25% and about 55% of the bed, the first portion comprising between about 4.5 and about 12.5 weight % cu~ric chloride and between about l.S and about 7 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about l.S:l and about 4 1, the second portion comprising between about 12 and about 25 weight %
cupric chloride and between about 0.5 and about 4 weight %
pota~ssium chloride, in a weight ratio of cupric chloride to potassi~m chloride of between ahout 5:1 and about 15:1;
(b) reacting the products of step (a) and a second portion of an oxygen-containing gas in a second reaction zone in contact with a second catalyst bed sub-stantially undiluted by catalytically inert particles and comprising cupric chloride and potassium chloride supported on spherical particles of activated alumina, the second catalyst bed being divided into two portions in the direction of flow of reactants therethrough, the first portion comprising between about 45% and about 75% of the bed, the second portion comprising between a~out 25% and about 55%
of the bed, the first portion of the bed comprising between about 5.5 and about 15 weight % cupric chloride and between about l and about 5 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about 2:1 and about 6:1, the second portion of the bed com-prising between about 12 and about 25 weight % cupric chloride - --and between about 0.5 and about 4 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between 5:1 and about 15:1; and, (c) reacting the products of step (b) and a third portion of an oxyqen-containing gas in a third reaction zone in contact with a third catalyst bed substantially undiluted by catalytically inert particles and comprising between about 12 and about 25 weight % cupric chloride and about 0.5 and about 4 weight % potassium chloride, supported on spherical particles of activated alumina, in a weight ratio of cupric chloride to potassium chloride of between about 5:1 and about 15:1.
In another aspect, this in~ention comprises a catalyst comprising cupric chloride and potassium chloride supported on a base comprising spherical particles of activated alumina, said base having a BET surface area of ~Q89879 between about 225 and about 275 m2/g, an attrition hardr.~ss of at least 90%, a total nitrogen pore volume of between about 0.3 and about 0.6 cc/g, an average pore diameter of between about 50 and about lO0 A, between about 20 and about 50% of the pore volume composed of pores having a diameter of between about 80 and 600 A and further characterized by an X-ray diffraction pattern as hereinafter defined and sub-stantially no observable grain boundaries after etching with HF.
In a third aspect, this invention comprises a reaction system for oxychlorination of ethylene in the presence of a catalyst comprising cupric and potassium chlorides supported on spherical particles of activated alumina, the reaction system comprising:
(a) a first reaction zone comprising a first catalyst bed divided into two portions in the direction of f low of reactants therethrough, the first portion comprising between about 45% and about 75% of the bed, the second portion comprising between about 25~ and about 55% of the bed, the first portion comprising between about 4.5 and about 12.5 weight % cupric chloride and between about 1.5 and about 7 weight % potassium chloride in a weight ratio of cupric chloride to potassium chloride of between about 1.5:1 and about 4:1, the second portion comprising between a~out 12 and about 25 weight % cupric chloride and between about 0.5 and about 4 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about 5:1 and about 15:1;
(b) a second reaction zone comprising a second catalyst bed divided into two portions in the direction of flow of reactants therethrough, the first portion comprising lQ8g879 between about 45% and about 75% of the bed, the second portion comprising between about 25% and about 55% of the bed, the first portion comprising between about 5.5 and about 15 weight % cupric chloride and between about 1 and about 5 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about 2:1 and about 6:1, the second portion of the bed comprising between about 12 and about 25 weight % cupric chloride and between about 0.5 and about 4 weight % potassium chloride, in a - -.
weight ratio of cupric chloride to potassium chloride of between about S:l and about 15:1;
(c) a third reaction zone comprising a third catalyst bed comprising between about 12 and about 25 weight % cupric chloride and between about 0.5 and about 4 weight potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about S:l and about lS:l.
Detailed Description of the Invention The invention will be described with reference to the Figure, which depicts an illustrative flow sheet for carrying out the process and utilizing the catalyst and system of the present invention.
The catalyst is prepared by conventional impreg-nation techni~ues utilizing a~ueous solutions of cupric and potassium chlorides, as further described in the examples which follow. The support which is impregnated as a spherical particulate high surface area activated alumina, that is, an alumina havlng a BET surface area of at least 100 m /g, preferably between about 225 and about 275 m /g, and also an attrition hardness of at least 90%, a total nitrogen pore ~olume of between about 0.3 and about 0.6 cc/g, and an average pore diameter of between about 50 andabout 100 A, wherein between about 20 and about 50% of the pore volume is composed of pores ha~ing a diameter of between about 80 and about 600 A. The alumina is further characterized by an X-ray diffraction pattern having three main peaks: diffuse peaks at 1.39 and 1.98 A and another peak at 2.34 A, the ratio of intensity of the peak at 1.39 A to that at 1.98 A
being between about 1.5:1 to about 5:1, and by showing sub-stantially no observable grain boundaries after etching with HF. Supports having these properties have been found to have good structural integrity even over lengthy periods of operation. Examples of suitable supports of this type are aluminas currently available under the designations HSC-ll ~, from Houdry Process and Chemical Company and SCM-250~, from Rhone-Progil.
As seen in the Figure, the process is conducted in three reactors in series, designated Rl, R2 and R3. Each of the reactors contains a catalyst bed, 12, 14, and 16 re-spectively. The reactors are preferably tubular reactors, having tubes packed with the catalyst. In reactor Rl, the catalyst bed is divided into two parts in the direction of the flow of reactants therethrough. The first part, at the inlet side of the reactor, comprises between about 45 and about 75%, preferably between about 5~ and about 65~, of the length of the catalyst bed and contains a catalyst having between about 4.5 and about 12.5, preferably between about ~ and a~out 8, and most preferably between about 5.5 and about 6.5 weight % cupric chloride, and between about 1.5 and about 7, preferably between about 2 and about 4, and most preferably between about 2.7 and 3.3 weight % potassium chloride, wherein the weight ratio of cupric chloride to potassium chlorideis between about 1.5:1 and 4:1, preferably between about 1.5:1 and 3:1, and most preferably about 2:1.
The second half of the bed, at the outlet end of the reactor, comprises correspondingly between about 25 and about 55%, preferably between about 35 and about 45%, of the bed length and contains a catalyst having between about 12 and about 25 weight %, preferably between about 15 and about 20 weight %, cupric chloride, between about 0.5 and about 4 weight %, preferably between about 1.5 and about 3 weight ~, of potassium chloride, the weight ratio of cupric to potassium chlorides being between about 5:1 and about 15:1, preferably between about 5:1 and about 12:1, most preferably about 10:1. Thus, the catalyst bed 12 of reactor Rl contains two types of catalysts: a first catalyst in the section of the bed towards the inlet, having a relatively lower activity in order to ensure that the reaction does not become uncontrollable in its early stages, and a second catalyst having a higher cupric chloride content and therefore, a higher activity, in the portion of the reactor towards the outlet, to continue the reaction at the point at which the reaction begins to lose vigor due to the consumption of oxygen.
~eactor R2 contains catalyst bed 14 which is also divided into two portions. The first portion of the catalyst bed, at the inlet side of the reactor, comprises between about 45 and about 75%, preferably between about 55 and about 65%, o~ the bed length and the second portion, toward the outlet end, comprises between about 25 and about 55%, preferably between about 35 and about 45%, correspondingly, of the bed length. The catalyst in the first portion of the bed 14 in reactor R2 can be somewhat stronger or more active than the catalyst in the first portion of the bed 12 in reactor ~1 -since the reaction has already proceeded partway towards completion. In reactor R2, the catalyst in the first portion of the bed contains between about 5.5 and about 15%, pre-ferably between about 7.5 and about 12.5%, and most preferably between about 9 and about 11 weight % cupric chloride, and between about 1 and about 5, preferably between about 1.5 and about 3.5, and most preferably between about 2.5 and about 3.5 weight % potassium chloride, the weight ratio of cupric chloride to potassium chloride being between about
2:1 and about 6:1, preferably between about 3:1 and about 4:1, most preferably about 10:3 (3.3:1). Similarly to reactor Rl, the second portion of the catalyst bed of reactor R2 contains a stronger catalyst, which has between about 12 and about 25 weight %, preferably between about 15 and about 20 weight %, cupric chloride and between about 0.5 and about 4 weight ~, preferably between about 1.5 and about 3 weight % potassium chloride, the weight ratio of cupric to potassium chloride being between about 5:1 and about 15:1, preferably between about 5:1 and about 12:1, most preferably about 10:1. Similar-ly to reactor Rl, since the reaction has been dropping in intensity as the gases pass through the catalyst bed, due to the consumption of oxygen, the danger of undesirably high localized temperatures in the portion of the bed nearest the outlet is much less than that in the portion near the inlet and therefore a more active catalyst can, and in fact should, be used for best conversions.
In both reactors Rl and R2, the weight ratio of potassium chloride to cupric chloride is preferably higher in the first portion of the catalyst bed than in the second portion.
~0 Entering reactor R3, the reaction has proceeded most of the way toward completion and ~here is much less ~()89879 danger of undesirably high localized temperatures in comPari-son to reactors Rl and R2. Therefore, the entire bed of reactor R3 can consist of the more active catalyst utilized in the lower sections of beds 12 and 14, that is a catalyst containing between about 12 and about 25 weight %, preferably between about 15 and about 20 weight % cupric chloride, and between about 0.5 and about 4 weight %, preferably between about 1.5 and about 3 weight ~, potassium chloride, with the weight ratio of cupric to potassium chlorides being between about 5:1 and about 15:1, preferably between about 5:1 and about 12:1, most preferably about 10:1. It may also be possible to utilize such a catalyst in reactor R3 and/or the portions of the catalyst beds 12, 16 nearest the outlet in reactors Rl and R2 with an even lower potassium chloride content and higher weight ratio of cupric to potassium chloride.
Tn the operation of the process of the present invention, hydrogen chloride qas is introduced through line 1 and preheated in preheater 22. Ethylene is introduced in line 2, preheated in preheater 21 and combined with the hydrogen chloride feed in line 1. An oxygen-containing gas, which may be air, molecular oxygen or oxygen-enriched air is introduced through line 3 and divided into three portions in lines 3a, 3b and 3c, respectively. The di~ision may be into three e~ual or unequal portions. The portion in line 3a is combined with the mixed hydrogen chloride ethylene feed in line 1 and introduced into reactor Rl through line 4.
The temperature of the mixed gaseous feed is generally about 120-220Oc~ preferably about 135-180C. The mixed feed passes through catalytic bed 12 which, as explained previously, preferably consists of catalyst pac~ed in tubes, and is with-drawn from the reactor in line 5.
10~9879 The products of reactor Rl in line S are com-bined with the second portion of oxygen-containing gas in line 3b, introduced into reactor R2 via line 6 and contacted with catalyst in bed 14. Reaction products are removed via line 7, contacted with a third portion of oxygen-containing gas in line 3c and introduced via line 8 into catalytic bed 16 of reactor R3. The reaction products are removed in line 9, preferably cooled in heat exchanger 23 and condensed in pro-duct condenser 24. The reaction products are recovered in line 10 and consist primarily of 1,2-dichloroethane, with small amounts of ethyl chloride and other chlorinated hydrocarbons.
In general, the process is carried out at an overall system pressure of between about 30 and about 100 psig, preferably between about 40 and about 90 psig. In order to maintain temperature control in reactors Rl, R2 and R3, these reactors are preferably constructed as jac~eted reactors, the jacket surrounding the tubes or catalystbedscontaining a heat exchange fluid such as boiling water, steam or Dowther ~ fluid. In general, the reaction is conducted at temperatures of between about 180 and about 340C, preferably between about 235 and about 300C. In reactor ~1' the hot spot temperature is generally maintained below about 330C, preferably below about 300C. In reactor R2, the hot spot temperature is maintained generally below 330C and preferably also below 300C and in reactor R3, the hot spot is maintained at generally below 320C, preferably below 300C. Another important factor is the control of the location of the hot spot in the reactors In each reactor, the hot spot should be located toward the inlet end of the catalyst bed. In reactors Rl and R2, the hot spot should, in fact, be located lQ89879 toward the inlet side in the first, or less active portion of the bed. If the hot spot occurs too far toward the outlet of the bed, it is an indication that the reaction is pro-ceeding too slowly in the bed, that is, that the catalyst is not being used efficiently. Additionally, if the hot spot occurs too far toward the outlet of the bed, it may produce a cumulative result with-the reaction-boosting effect of the stronger catalyst in the second portion of the bed, resulting in an undesirably high temperature level at that point.
The division of the oxygen-containing gas among lines 3a, 3b and 3c can be performed such that equal amounts enter all three reactors or, as desired, the amount entering each reactor can be varied as is known in the art. A variance in the amount of this gas introduced into each reactor can effect the temperature and the location of the hot spot in the reactor.
For purposes of illustration, the Figure depicts a system in which all three reactors are of the downflow type;
that is, reactants are introduced at the top of the reactors and products withdrawn at the bottom. The invention may, however, be practiced in either downflow or upflow reactors, with suitable catalyst hold-down devices utilized for upf~ow reactors. Construction of the reactors as alternately down-flow and upflow may reduce piping costs. Thus, reactors R
and R3 could be upflow reactors and reactor R2 a downflow one. Conversely, reactors R1 and R3 could be downflow and R2 upflow.
The hydrogen chloride feed need not all be introduced into the first reactor; a portion may be split off and introduced into reactor R2, with the second portion of the oxyge~-containing gas.
In general, the process is operated with an excess of both oxygen-containing gas and ethylene with respect to hydrogen chloride in order to ensure as complete conversion of hydrogen chloride as possible. When using air, it is desirable to maintain as low an excess of these reactants as possible in order to avoid the handling of large amounts of gas. In such case, the ethylene excess is maintained at a maximum of about 35%, preferably between about 5 and about 20~, and the air excess is maintained at a maximum of about 25%, preferably between about 5 and about 20%.
The invention is described herein primarily in the context of an oxychlorination process in which the oxygen-containing gas is air. However, the catalyst, system and process herein described are also suitable for use in an operation in which molecular oxygen or oxygen-enriched air is employed. In one such process, as described in U.S. Patent
In both reactors Rl and R2, the weight ratio of potassium chloride to cupric chloride is preferably higher in the first portion of the catalyst bed than in the second portion.
~0 Entering reactor R3, the reaction has proceeded most of the way toward completion and ~here is much less ~()89879 danger of undesirably high localized temperatures in comPari-son to reactors Rl and R2. Therefore, the entire bed of reactor R3 can consist of the more active catalyst utilized in the lower sections of beds 12 and 14, that is a catalyst containing between about 12 and about 25 weight %, preferably between about 15 and about 20 weight % cupric chloride, and between about 0.5 and about 4 weight %, preferably between about 1.5 and about 3 weight ~, potassium chloride, with the weight ratio of cupric to potassium chlorides being between about 5:1 and about 15:1, preferably between about 5:1 and about 12:1, most preferably about 10:1. It may also be possible to utilize such a catalyst in reactor R3 and/or the portions of the catalyst beds 12, 16 nearest the outlet in reactors Rl and R2 with an even lower potassium chloride content and higher weight ratio of cupric to potassium chloride.
Tn the operation of the process of the present invention, hydrogen chloride qas is introduced through line 1 and preheated in preheater 22. Ethylene is introduced in line 2, preheated in preheater 21 and combined with the hydrogen chloride feed in line 1. An oxygen-containing gas, which may be air, molecular oxygen or oxygen-enriched air is introduced through line 3 and divided into three portions in lines 3a, 3b and 3c, respectively. The di~ision may be into three e~ual or unequal portions. The portion in line 3a is combined with the mixed hydrogen chloride ethylene feed in line 1 and introduced into reactor Rl through line 4.
The temperature of the mixed gaseous feed is generally about 120-220Oc~ preferably about 135-180C. The mixed feed passes through catalytic bed 12 which, as explained previously, preferably consists of catalyst pac~ed in tubes, and is with-drawn from the reactor in line 5.
10~9879 The products of reactor Rl in line S are com-bined with the second portion of oxygen-containing gas in line 3b, introduced into reactor R2 via line 6 and contacted with catalyst in bed 14. Reaction products are removed via line 7, contacted with a third portion of oxygen-containing gas in line 3c and introduced via line 8 into catalytic bed 16 of reactor R3. The reaction products are removed in line 9, preferably cooled in heat exchanger 23 and condensed in pro-duct condenser 24. The reaction products are recovered in line 10 and consist primarily of 1,2-dichloroethane, with small amounts of ethyl chloride and other chlorinated hydrocarbons.
In general, the process is carried out at an overall system pressure of between about 30 and about 100 psig, preferably between about 40 and about 90 psig. In order to maintain temperature control in reactors Rl, R2 and R3, these reactors are preferably constructed as jac~eted reactors, the jacket surrounding the tubes or catalystbedscontaining a heat exchange fluid such as boiling water, steam or Dowther ~ fluid. In general, the reaction is conducted at temperatures of between about 180 and about 340C, preferably between about 235 and about 300C. In reactor ~1' the hot spot temperature is generally maintained below about 330C, preferably below about 300C. In reactor R2, the hot spot temperature is maintained generally below 330C and preferably also below 300C and in reactor R3, the hot spot is maintained at generally below 320C, preferably below 300C. Another important factor is the control of the location of the hot spot in the reactors In each reactor, the hot spot should be located toward the inlet end of the catalyst bed. In reactors Rl and R2, the hot spot should, in fact, be located lQ89879 toward the inlet side in the first, or less active portion of the bed. If the hot spot occurs too far toward the outlet of the bed, it is an indication that the reaction is pro-ceeding too slowly in the bed, that is, that the catalyst is not being used efficiently. Additionally, if the hot spot occurs too far toward the outlet of the bed, it may produce a cumulative result with-the reaction-boosting effect of the stronger catalyst in the second portion of the bed, resulting in an undesirably high temperature level at that point.
The division of the oxygen-containing gas among lines 3a, 3b and 3c can be performed such that equal amounts enter all three reactors or, as desired, the amount entering each reactor can be varied as is known in the art. A variance in the amount of this gas introduced into each reactor can effect the temperature and the location of the hot spot in the reactor.
For purposes of illustration, the Figure depicts a system in which all three reactors are of the downflow type;
that is, reactants are introduced at the top of the reactors and products withdrawn at the bottom. The invention may, however, be practiced in either downflow or upflow reactors, with suitable catalyst hold-down devices utilized for upf~ow reactors. Construction of the reactors as alternately down-flow and upflow may reduce piping costs. Thus, reactors R
and R3 could be upflow reactors and reactor R2 a downflow one. Conversely, reactors R1 and R3 could be downflow and R2 upflow.
The hydrogen chloride feed need not all be introduced into the first reactor; a portion may be split off and introduced into reactor R2, with the second portion of the oxyge~-containing gas.
In general, the process is operated with an excess of both oxygen-containing gas and ethylene with respect to hydrogen chloride in order to ensure as complete conversion of hydrogen chloride as possible. When using air, it is desirable to maintain as low an excess of these reactants as possible in order to avoid the handling of large amounts of gas. In such case, the ethylene excess is maintained at a maximum of about 35%, preferably between about 5 and about 20~, and the air excess is maintained at a maximum of about 25%, preferably between about 5 and about 20%.
The invention is described herein primarily in the context of an oxychlorination process in which the oxygen-containing gas is air. However, the catalyst, system and process herein described are also suitable for use in an operation in which molecular oxygen or oxygen-enriched air is employed. In one such process, as described in U.S. Patent
3,892,816, a large excess of ethylene is utilized with respect to the oxygen and hydrogen chloride to prevent over-reaction and excessively high hot spots. The excess ethyleneis preferably recovered from the reaction product, and recycled to the oxychlorination reactors; thus in such a process, minimizationofethylene excess is not an objective.
If steel equipment is utilized in the hydro~en chloride flow circuit, small amounts of ferric chloride may be formed and introduced into the catalyst with the feed stream. Corrosion of the oxygen-containing gas supply system can produce iron oxides which can be converted to ferric chloride by reaction with hydrogen chloride in the reactor. The catalyst may contain minor amounts of iron as impurities; however, it has been found that additional ferric chloride, even in small amounts, tends to contaminate and deactivate a cupric chloride oxychlorination catalyst.
In one embodiment of the present invention, therefore, ferric chloride contamination of the catalyst is avoided, as shown in the copending U.S. Patent 4,000,205 to Ramsey G. Campbell, entitled "Purification of Gas Streams Containing Ferric Chloride'' by passing either the hydrogen chloride stream or the mixed gaseous feed stream through a bed of activated alumina impregnated with between about 5 and about 25, preferably between about 10 and about 20 weight % sodium chloride or potassium chloride. ~he bed may be placed in the hydrogen chloride line 1, either before or after preheater 22, or in the combined feed line 4. Alternatively, it may be located inside Rl at the space 30 adjacent the inlet. In a preferred embodiment, in which tubular reactors are utilized, the bed material may be loaded into the portions of the tubes of reactor Rl adjacent the inlet, ahead of the cupric chloride catalyst in the direction of flow of reactants, and may be separated from it by a screen or the like to prevent migration of removed ferric chloride into the cupric chloride catalyst.
In a preferred embodiment, the alumina utilized is the same as that utilized as the catalyst support.
~ t should be noted that the operation of each of the reactors Rl and R2 is only partially affected by the operation of the other. Thus, for instance, should the location or temperature of the hot spot in either of reactors ; Rl and R2 be temporarily outside the desired range, the operation of the other reactor would not necessarily be adversely affected or, if it were, it could be possible to separately control operation by adjusting the coolant temper-ature, di~ision of air between the reactors, etc. Similarly, 1~89879 it is possible, though much less preferred, to utilize the catalyst disclosed herein in the disclosed proportions and bed divisions, in either of reactors Rl or R2 and another suitable, though probably less effective catalyst, in the other. Such an arrangement would not be expected to possess all the advantages of the present invention in terms of throughput, pressure drop, conversion, selectivity, etc., but may be necessary in the event of an emergency or temporary unavailability of catalyst.
To further illustrate the invention in its various embodiments and modifications, the following examples are presented. These in no way are intended to limit the in-vention, but merely to serve as illustrations thereof.
Catalyst Preparation The catalysts utilized in the following examples were prepared as follows:
A quantity of dry unimpregnated spherically shaped alumina particles was placed in a beaker and weighed. The alumina utilized was HSC-114~ alumina obtained from Houdry 20 Process and Chemical Company, and had the following properties:
Surface Area, BET 250 + 25 m2/g Bulk Density 37-44 lb/cu. ft.
Loss of Ignition (300C) 5 wt. %, max.
Attrition ~ardness 90%, min.
Pore Volume, N 0.44 cc/g Average Pore Diameter, BET 64-70 A
Pore Volume, 80-600 A Pores -- 20-37% of total pore volume Screen Analysis (Tyler Screen) + 3 mesh 1.0 max. wt. ~ -- 3, + 4 mesh 25-70 wt.
If steel equipment is utilized in the hydro~en chloride flow circuit, small amounts of ferric chloride may be formed and introduced into the catalyst with the feed stream. Corrosion of the oxygen-containing gas supply system can produce iron oxides which can be converted to ferric chloride by reaction with hydrogen chloride in the reactor. The catalyst may contain minor amounts of iron as impurities; however, it has been found that additional ferric chloride, even in small amounts, tends to contaminate and deactivate a cupric chloride oxychlorination catalyst.
In one embodiment of the present invention, therefore, ferric chloride contamination of the catalyst is avoided, as shown in the copending U.S. Patent 4,000,205 to Ramsey G. Campbell, entitled "Purification of Gas Streams Containing Ferric Chloride'' by passing either the hydrogen chloride stream or the mixed gaseous feed stream through a bed of activated alumina impregnated with between about 5 and about 25, preferably between about 10 and about 20 weight % sodium chloride or potassium chloride. ~he bed may be placed in the hydrogen chloride line 1, either before or after preheater 22, or in the combined feed line 4. Alternatively, it may be located inside Rl at the space 30 adjacent the inlet. In a preferred embodiment, in which tubular reactors are utilized, the bed material may be loaded into the portions of the tubes of reactor Rl adjacent the inlet, ahead of the cupric chloride catalyst in the direction of flow of reactants, and may be separated from it by a screen or the like to prevent migration of removed ferric chloride into the cupric chloride catalyst.
In a preferred embodiment, the alumina utilized is the same as that utilized as the catalyst support.
~ t should be noted that the operation of each of the reactors Rl and R2 is only partially affected by the operation of the other. Thus, for instance, should the location or temperature of the hot spot in either of reactors ; Rl and R2 be temporarily outside the desired range, the operation of the other reactor would not necessarily be adversely affected or, if it were, it could be possible to separately control operation by adjusting the coolant temper-ature, di~ision of air between the reactors, etc. Similarly, 1~89879 it is possible, though much less preferred, to utilize the catalyst disclosed herein in the disclosed proportions and bed divisions, in either of reactors Rl or R2 and another suitable, though probably less effective catalyst, in the other. Such an arrangement would not be expected to possess all the advantages of the present invention in terms of throughput, pressure drop, conversion, selectivity, etc., but may be necessary in the event of an emergency or temporary unavailability of catalyst.
To further illustrate the invention in its various embodiments and modifications, the following examples are presented. These in no way are intended to limit the in-vention, but merely to serve as illustrations thereof.
Catalyst Preparation The catalysts utilized in the following examples were prepared as follows:
A quantity of dry unimpregnated spherically shaped alumina particles was placed in a beaker and weighed. The alumina utilized was HSC-114~ alumina obtained from Houdry 20 Process and Chemical Company, and had the following properties:
Surface Area, BET 250 + 25 m2/g Bulk Density 37-44 lb/cu. ft.
Loss of Ignition (300C) 5 wt. %, max.
Attrition ~ardness 90%, min.
Pore Volume, N 0.44 cc/g Average Pore Diameter, BET 64-70 A
Pore Volume, 80-600 A Pores -- 20-37% of total pore volume Screen Analysis (Tyler Screen) + 3 mesh 1.0 max. wt. ~ -- 3, + 4 mesh 25-70 wt.
- 4, + 5 mesh 25-70 wt. %
- 5, + 6 mesh 10 max. wt. %
- 6 mesh 3 max. wt. %
X-ray diffraction data showed three main peaks:
at 1.39, 1.98 and 2.34 A. The peaks at 1.39 and 1.98 A
were diffuse. The X-ray diffraction pattern of gamma-alumina, as given in ASTM file 10-425, has main peaks at the same values. Xowever, ASTM File 10-425 shows the intensities of the peaks at 1.39 and 1.98 A to be about equal, whereas the diffraction data for the catalysts used in these examples shows the intensity of the peak at 1. 39 A to be about twice that of the 1.9 8 A peak.
Results of this type indicate that the support is comprised of (crystalline) gamma-alumina plus an amorphous form of alumina. The amorphous form is possibly rho-alumina, the X-ray diffraction pattern of which has a single broad band at 1.40 A.
Purther investigation of the catalyst's micro-structure was performed by HF etching. Samples of new andused catalyst were mounted on a special szmple holder and imbedded in an epoxide resin. The samples were cut and polished and chemically etched on a cross-section for 2-5 minutes at room temperature with a 20~ HF solution. Ob-servations were made after 20 sec. and 4 minutes at 21X, and after S minutes at 85X. ~o evidence of grain boundaries was observed even after 12 minutes of etching.
Water was added to the bea~er in small amounts, the contents being stirred with a glass rod after each addition, until moisture was observed in the bea~er. At that point, the alumina was saturated with water. From the 1(~89879 final weight of the beaker, the percentage by weight of the absorbed water can be derived. Thus, the amount of water by weight absorbed by the chosen weight of base is determined.
The ~uantity of dry alumina base to be impregnated was weighed. The quantities of cupric and potassium chlorides which constituted the desired weight percent with reference to the dry base were weighed and dissolved in water. Additional water was added to the resulting solution to bring the volume up to the absorptive capacity of the base as previously determined. It should be noted that it may be necessary to reduce this volume by about 3% to prevent there being a large excess of impregnating solution which is not absorbed by the base. The base and impregnating solution were placed in a drum which was covered, sealed, and rotated for a period of 15 minutes to achieve impregnation.
After 15 minutes, the drum was removed, immediately opened and the saturated alumina particles placed in either glass or ceramic trays to a depth of approximately three inches. The trays were placed in a forced draft oven where the temperature was maintained at 140C for 16 to 24 hours.
The catalyst was then removed and allowed to cool prior to being stored in air-tight containers.
The weight percents of the salts in the catalyst thus prepared are within ~.5% of the desired values. The accuracy can be enhanced by thorough drying of the alumina base prior to weighing. ~rying should immediately follow impregnation; a delay can be detrimental to the physical structure o~ the resulting catalyst.
The experimental data in the tables which follow was obtained using catalysts prepared according to the fore-going procedure in an apparatus arranged in a flow se~uence 1(!898~79 as in the Figure. The three reactors, Rl, R2 and R3, each consisted of one schedule 40 nickel pipe, 12.5 feet long and 1 inch in diameter, jacketed for the entire length with a 2-1/2 inch schedule 40 steel pipe, and arranged for downward flow of reactants. The heat of reaction was removed by re-fluxing Dowtherm~ E in the annular space between the two pipes. The hot spot temper~ture and location inside the catalytic bed of each reactor was measured by means of a mo~able thermocouple inside a 12-foot long thermowell which was introduced at the bottom of each reactor.
As shown in the Figure, hydrogen chloride was introduced into the system in line 1 through a preheater 22.
Ethylene was introduced into the system in line 2 through a preheater 21. Air was introduced into line 3 and split into subconduits 3a, 3b and 3c, the air in line 3a being introduced - into reactor Rl, that in 3b into reactor R2, and that in 3c into reactor ~3. The mixed feed to reactor Rl af~er preheating was at a temperature of about 140C. A 100% throughput basis was established as being equivalent to a hydrogen chloride mass velocity in the reactor of 117.6 g.-mole/h-in.2. The air and ethylene feed rates are expressed as a percentage excess based on hydrogen chloride, assuming a stoichiometric reaction to produce 1,2-dichloroethane.
The gas exiting from reactor ~3, after pressure reduction, was cooled in a glass water-cooled condenser which condensed all the unreacted hydrogen chloride as an aqueous Fhase and the majority of the 1,2-dichloroethane produced as a relatively pure (about 98.5%) organic phase. Hydrogen chloride conversion was determined by titrating the aqueous 3Q phase with sodium hydroxide to obtain its hydrogen chloride concentration in weight percent.
The condensed gas from the water-cooled condenser was analyzed by gas chromatography. The analyses were used to calculate the amount of ethylene oxidation and formation of ethyl chloride, both expressed as a percentage of the ethylene feed.
Table I illustrates conditions of one run of the process according to the present invention, in a preferred embodiment. The run, which continued for a total of 320 hours, was divided into two sections~ In the first section, occupying the first 298 hours, the equipment was operated at a 125%
throughput of hydrogen chloride and other reactants. During ~-the last 22 hours, the equipment was operated at a 100 throughput rate.
The catalyst to be used was prepared in three formulations. These are shown in Table I as catalysts A, -B and C. The desired weight percents of cupric and potassium chlorides were:
Catalyst A: 6.0 + 0.5% CuC12 3.0 + 0.3~ KCl (weight ratio 2:1) Catalyst B: 10.0 + 0.7% CuC12 3.0 + 0.3% KCl (weight ratio 3.3:1) Catalyst C: 18.0 + 1.8% CuC12 1.8 + ~.25% KCl (weight ratio 10:1~
(Table ~ shows the amounts found to be present after analysis of the catalysts. The amounts of cupric and potassium chloride in catalyst C varied somewhat because catalysts from several different preparations were used). In all three reactors, the catalyst bed length was 135 inches; the first (upper) portion, being 81 inches (60~ of bed length) and the second 10~9879 (lower) portion being 54 inches in length, or 40~ of the total bed length. Catalyst A was utilized in the first portion of the reactor Rl (bed 12); catalyst B was utilized in the first portion of reactor R2 (bed 14): catalyst C was utilized in reactor R3 and the lower portions of reactors Rl and R2.
TABLE I
Catalyst: A B C
Cupric Chloride - wt.% 6.1 9.9 18.4-19.6 -~
Potassium Chloride - wt.% 3.08 3.08 1.84-1.92 Iron as Fe - ppm ~800 C800 ~800 Sulfate as SO4 - wt.~ C0.5 ~0.5 <0.5 Silica as SiO2 - wt.% ~0.25 <0.25 C0.25 Loss on Ignition at 300C - wt.~ ~6.0 ~6.0 ~6.0 Hardness - wt.% 93 min. 94 95 Screen Analysis - wt.%
+3 3 max. 3 max. 3 max.
+4 40 min. 40 min. 40 min.
~5 45 max. 45 max. 45 max.
+6 5 max. 5 max. 5 max.
BET Surface Area - m /g 204 196.5 149-165 Total N2 Pore Volume - cc/g ~0.25 >0.25 >0.25 Pore Volume 80-600A
Pores - % of total pore volume ~30 ~30 ~30 Average Pore Diameter (BET) - A ~60 >60 ~60 During the first 60 hours of the run, various sources which produced unstable data were corrected and stabilized. Similarly, hours 265 through 298, which occurred between the two portions of the overall run, were occupied by restabilizing the pilot plant following a one-month shut-down between portions of the run.
During operation, as can be seen from the follow-ing table, variations were made in the total system pressure, air and ethylene excesses, and division of air between the three reactors, in order to determine the effect of these conditions on hydrogen chloride conversion, selectivity of the reaction to 1,2-dichloroethane, and hot spot temperature and location. The run data and results are given in the following Table II.
. - 26 -1(~89879 .
,~ ~ ~ ~ ~ ~ I ~ ~ N ~ ~ N ~
~ 3 ~ ~ ~ N ~
O o l ~D a~ co ~ co ~ ~ I~ c~ 1~ ~ o ~ co ~ o~
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, :
Similarly to run number 1 described hereinabove, additional runs designated in Table III below as runs 2 through ~ -9, were conducted utilizing various combinations of catalyst compositions and reaction conditions within the scope of this invention. In all cases, as was the case in run number 1, the catalyst bed was 135 inches long. In both Rl and R2, the first zone, at the upper, or inlet, end of the reactor occupied 81 inches, or 60% of the bed, while the second zone occupied 54 inches, or 40% of the total bed length. The catalyst in reactor R3 was similar to that in run number 1. Coolant temperatures were maintained similarly to run number 1.
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10~9~79 In all the runs 1 through 9 above, it can be seen that the use of the catalyst described herein, in the staging patterns described, resulted in maintenance of hot spot temperatures generally below about 340C at throughputs as high as 125~ of the design throughput. The hot spots were in con-trollable locations and, in fact, as can be seen, on many occasions they fell far below 300~C. Of e~ual importance, the pressure drop remained substantially constant throughout the reaction system, even in run 1, in which the run length totaled over 300 hours. Thus, a pressure reduction was not required to maintain the hot spot control and the pressure drop did not increase over extended run times due to deterioration of the catalyst. Furthermore, even when operating at high throughput, the ethylene excess could be kept within reasonable limits with-out substantially affecting hydrogen chloride conversion. As seen from the data in Tables II and III, it was quite possible to operate at ethylene excesses of about 10% while still obtaining as high as 99+% hydrogen chloride conversion.
Additionally, the catalyst in the staging pattern, herein described, has also been found suitable for operation at less than design throughput. Thus the catalyst and system herein described possesses versatility and can be utilized in a plant operation in which the throughput can be variable, depending on conditions such as feedstock supply and mar~et demand, over a range from substantially less than design capacity to substantially greater than design capacity, without xequiring replacement or modification.
X-ray diffraction data showed three main peaks:
at 1.39, 1.98 and 2.34 A. The peaks at 1.39 and 1.98 A
were diffuse. The X-ray diffraction pattern of gamma-alumina, as given in ASTM file 10-425, has main peaks at the same values. Xowever, ASTM File 10-425 shows the intensities of the peaks at 1.39 and 1.98 A to be about equal, whereas the diffraction data for the catalysts used in these examples shows the intensity of the peak at 1. 39 A to be about twice that of the 1.9 8 A peak.
Results of this type indicate that the support is comprised of (crystalline) gamma-alumina plus an amorphous form of alumina. The amorphous form is possibly rho-alumina, the X-ray diffraction pattern of which has a single broad band at 1.40 A.
Purther investigation of the catalyst's micro-structure was performed by HF etching. Samples of new andused catalyst were mounted on a special szmple holder and imbedded in an epoxide resin. The samples were cut and polished and chemically etched on a cross-section for 2-5 minutes at room temperature with a 20~ HF solution. Ob-servations were made after 20 sec. and 4 minutes at 21X, and after S minutes at 85X. ~o evidence of grain boundaries was observed even after 12 minutes of etching.
Water was added to the bea~er in small amounts, the contents being stirred with a glass rod after each addition, until moisture was observed in the bea~er. At that point, the alumina was saturated with water. From the 1(~89879 final weight of the beaker, the percentage by weight of the absorbed water can be derived. Thus, the amount of water by weight absorbed by the chosen weight of base is determined.
The ~uantity of dry alumina base to be impregnated was weighed. The quantities of cupric and potassium chlorides which constituted the desired weight percent with reference to the dry base were weighed and dissolved in water. Additional water was added to the resulting solution to bring the volume up to the absorptive capacity of the base as previously determined. It should be noted that it may be necessary to reduce this volume by about 3% to prevent there being a large excess of impregnating solution which is not absorbed by the base. The base and impregnating solution were placed in a drum which was covered, sealed, and rotated for a period of 15 minutes to achieve impregnation.
After 15 minutes, the drum was removed, immediately opened and the saturated alumina particles placed in either glass or ceramic trays to a depth of approximately three inches. The trays were placed in a forced draft oven where the temperature was maintained at 140C for 16 to 24 hours.
The catalyst was then removed and allowed to cool prior to being stored in air-tight containers.
The weight percents of the salts in the catalyst thus prepared are within ~.5% of the desired values. The accuracy can be enhanced by thorough drying of the alumina base prior to weighing. ~rying should immediately follow impregnation; a delay can be detrimental to the physical structure o~ the resulting catalyst.
The experimental data in the tables which follow was obtained using catalysts prepared according to the fore-going procedure in an apparatus arranged in a flow se~uence 1(!898~79 as in the Figure. The three reactors, Rl, R2 and R3, each consisted of one schedule 40 nickel pipe, 12.5 feet long and 1 inch in diameter, jacketed for the entire length with a 2-1/2 inch schedule 40 steel pipe, and arranged for downward flow of reactants. The heat of reaction was removed by re-fluxing Dowtherm~ E in the annular space between the two pipes. The hot spot temper~ture and location inside the catalytic bed of each reactor was measured by means of a mo~able thermocouple inside a 12-foot long thermowell which was introduced at the bottom of each reactor.
As shown in the Figure, hydrogen chloride was introduced into the system in line 1 through a preheater 22.
Ethylene was introduced into the system in line 2 through a preheater 21. Air was introduced into line 3 and split into subconduits 3a, 3b and 3c, the air in line 3a being introduced - into reactor Rl, that in 3b into reactor R2, and that in 3c into reactor ~3. The mixed feed to reactor Rl af~er preheating was at a temperature of about 140C. A 100% throughput basis was established as being equivalent to a hydrogen chloride mass velocity in the reactor of 117.6 g.-mole/h-in.2. The air and ethylene feed rates are expressed as a percentage excess based on hydrogen chloride, assuming a stoichiometric reaction to produce 1,2-dichloroethane.
The gas exiting from reactor ~3, after pressure reduction, was cooled in a glass water-cooled condenser which condensed all the unreacted hydrogen chloride as an aqueous Fhase and the majority of the 1,2-dichloroethane produced as a relatively pure (about 98.5%) organic phase. Hydrogen chloride conversion was determined by titrating the aqueous 3Q phase with sodium hydroxide to obtain its hydrogen chloride concentration in weight percent.
The condensed gas from the water-cooled condenser was analyzed by gas chromatography. The analyses were used to calculate the amount of ethylene oxidation and formation of ethyl chloride, both expressed as a percentage of the ethylene feed.
Table I illustrates conditions of one run of the process according to the present invention, in a preferred embodiment. The run, which continued for a total of 320 hours, was divided into two sections~ In the first section, occupying the first 298 hours, the equipment was operated at a 125%
throughput of hydrogen chloride and other reactants. During ~-the last 22 hours, the equipment was operated at a 100 throughput rate.
The catalyst to be used was prepared in three formulations. These are shown in Table I as catalysts A, -B and C. The desired weight percents of cupric and potassium chlorides were:
Catalyst A: 6.0 + 0.5% CuC12 3.0 + 0.3~ KCl (weight ratio 2:1) Catalyst B: 10.0 + 0.7% CuC12 3.0 + 0.3% KCl (weight ratio 3.3:1) Catalyst C: 18.0 + 1.8% CuC12 1.8 + ~.25% KCl (weight ratio 10:1~
(Table ~ shows the amounts found to be present after analysis of the catalysts. The amounts of cupric and potassium chloride in catalyst C varied somewhat because catalysts from several different preparations were used). In all three reactors, the catalyst bed length was 135 inches; the first (upper) portion, being 81 inches (60~ of bed length) and the second 10~9879 (lower) portion being 54 inches in length, or 40~ of the total bed length. Catalyst A was utilized in the first portion of the reactor Rl (bed 12); catalyst B was utilized in the first portion of reactor R2 (bed 14): catalyst C was utilized in reactor R3 and the lower portions of reactors Rl and R2.
TABLE I
Catalyst: A B C
Cupric Chloride - wt.% 6.1 9.9 18.4-19.6 -~
Potassium Chloride - wt.% 3.08 3.08 1.84-1.92 Iron as Fe - ppm ~800 C800 ~800 Sulfate as SO4 - wt.~ C0.5 ~0.5 <0.5 Silica as SiO2 - wt.% ~0.25 <0.25 C0.25 Loss on Ignition at 300C - wt.~ ~6.0 ~6.0 ~6.0 Hardness - wt.% 93 min. 94 95 Screen Analysis - wt.%
+3 3 max. 3 max. 3 max.
+4 40 min. 40 min. 40 min.
~5 45 max. 45 max. 45 max.
+6 5 max. 5 max. 5 max.
BET Surface Area - m /g 204 196.5 149-165 Total N2 Pore Volume - cc/g ~0.25 >0.25 >0.25 Pore Volume 80-600A
Pores - % of total pore volume ~30 ~30 ~30 Average Pore Diameter (BET) - A ~60 >60 ~60 During the first 60 hours of the run, various sources which produced unstable data were corrected and stabilized. Similarly, hours 265 through 298, which occurred between the two portions of the overall run, were occupied by restabilizing the pilot plant following a one-month shut-down between portions of the run.
During operation, as can be seen from the follow-ing table, variations were made in the total system pressure, air and ethylene excesses, and division of air between the three reactors, in order to determine the effect of these conditions on hydrogen chloride conversion, selectivity of the reaction to 1,2-dichloroethane, and hot spot temperature and location. The run data and results are given in the following Table II.
. - 26 -1(~89879 .
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, :
Similarly to run number 1 described hereinabove, additional runs designated in Table III below as runs 2 through ~ -9, were conducted utilizing various combinations of catalyst compositions and reaction conditions within the scope of this invention. In all cases, as was the case in run number 1, the catalyst bed was 135 inches long. In both Rl and R2, the first zone, at the upper, or inlet, end of the reactor occupied 81 inches, or 60% of the bed, while the second zone occupied 54 inches, or 40% of the total bed length. The catalyst in reactor R3 was similar to that in run number 1. Coolant temperatures were maintained similarly to run number 1.
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10~9~79 In all the runs 1 through 9 above, it can be seen that the use of the catalyst described herein, in the staging patterns described, resulted in maintenance of hot spot temperatures generally below about 340C at throughputs as high as 125~ of the design throughput. The hot spots were in con-trollable locations and, in fact, as can be seen, on many occasions they fell far below 300~C. Of e~ual importance, the pressure drop remained substantially constant throughout the reaction system, even in run 1, in which the run length totaled over 300 hours. Thus, a pressure reduction was not required to maintain the hot spot control and the pressure drop did not increase over extended run times due to deterioration of the catalyst. Furthermore, even when operating at high throughput, the ethylene excess could be kept within reasonable limits with-out substantially affecting hydrogen chloride conversion. As seen from the data in Tables II and III, it was quite possible to operate at ethylene excesses of about 10% while still obtaining as high as 99+% hydrogen chloride conversion.
Additionally, the catalyst in the staging pattern, herein described, has also been found suitable for operation at less than design throughput. Thus the catalyst and system herein described possesses versatility and can be utilized in a plant operation in which the throughput can be variable, depending on conditions such as feedstock supply and mar~et demand, over a range from substantially less than design capacity to substantially greater than design capacity, without xequiring replacement or modification.
Claims (3)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for oxychlorination of a feed selected from the group consisting of ethylene and partially chlorinated derivatives thereof, comprising reacting said feed with hydro-gen chloride and an oxygen-containing gas in contact with a fixed bed of a catalyst substantially undiluted by catalytical-ly inert particles and comprising cupric chloride and potassium chloride supported on spherical particles of activated alumina, the catalyst bed being divided into two portions in the direc-tion of flow of reactants therethrough, the first portion comprising between about 45% and about 75% of the bed, the second portion comprising between about 25% and about 55% of the bed, the first portion comprising between about 5.5 and about 15 weight % cupric chloride and between about 1 and about 5 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about 2:1 and about 6:1, the second portion of the bed comprising be-tween about 12 and about 25 weight % cupric chloride and between about 0.5 and about 4 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about 5:1 and about 15:1.
2. A process according to Claim 1 in which the first portion of the bed comprises between about 7.5 and about 12.5 weight % cupric chloride and between about 1.5 and about 3.5 weight % potassium chloride, in a weight ratio of cupric chloride to potassium chloride of between about
3:1 and about 4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA339,794A CA1089879A (en) | 1975-07-14 | 1979-11-14 | Oxychlorination of ethylene |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59546575A | 1975-07-14 | 1975-07-14 | |
| US595,465 | 1975-07-14 | ||
| US05/686,333 US4123467A (en) | 1975-07-14 | 1976-05-14 | Oxychlorination of ethylene |
| US686,333 | 1976-05-14 | ||
| CA256,092A CA1079258A (en) | 1975-07-14 | 1976-06-30 | Oxychlorination of ethylene |
| CA339,794A CA1089879A (en) | 1975-07-14 | 1979-11-14 | Oxychlorination of ethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089879A true CA1089879A (en) | 1980-11-18 |
Family
ID=27425927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA339,794A Expired CA1089879A (en) | 1975-07-14 | 1979-11-14 | Oxychlorination of ethylene |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1089879A (en) |
-
1979
- 1979-11-14 CA CA339,794A patent/CA1089879A/en not_active Expired
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