CA1111454A - Preparation of vinyl chloride - Google Patents
Preparation of vinyl chlorideInfo
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- CA1111454A CA1111454A CA317,242A CA317242A CA1111454A CA 1111454 A CA1111454 A CA 1111454A CA 317242 A CA317242 A CA 317242A CA 1111454 A CA1111454 A CA 1111454A
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Abstract
PREPARATION OF VINYL CHLORIDE
ABSTRACT OF THE DISCLOSURE
Monohalogenated olefins are selectively prepared in high high yields from alkanes having 2 to 4 carbon atoms from un-saturated hydrocarbons or from halo-alkanes by the reaction with a hydrogen halide and a source of oxygen at a temperature from about 200° to about 700°C in contact with a catalyst com-prising a copper halide and an alkali metal phosphate, particu-larly potassium phosphate, deposited on an inorganic support.
Typically, vinyl chloride is prepared in one step from ethane, ethylene or ethylchloride.
ABSTRACT OF THE DISCLOSURE
Monohalogenated olefins are selectively prepared in high high yields from alkanes having 2 to 4 carbon atoms from un-saturated hydrocarbons or from halo-alkanes by the reaction with a hydrogen halide and a source of oxygen at a temperature from about 200° to about 700°C in contact with a catalyst com-prising a copper halide and an alkali metal phosphate, particu-larly potassium phosphate, deposited on an inorganic support.
Typically, vinyl chloride is prepared in one step from ethane, ethylene or ethylchloride.
Description
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.: :
PREPARATION OF VINYL CHLORIDE
The present application relates, in one embodiment, to the conversion of alkanes to unsaturated halogenated products such as vinyl halides. More particularly, in that embodiment, it relates to the conversion of ethane directly to vinyl chlor-ide in high yields by the oxychlorination reaction utilizing a highly selective catalyst.
The conversion of hydrocarbons unsaturated hydro-carbons or haloalkanes to useful halogenated hydrocarbons by the so-called "oxychlorination" reaction, i.e., the reaction of ` the hydrocarbon, a hydrogen halide as the source of the halogen and a source of elemental oxygen, in the presence of copper con-; taining catalysts is well known in the art. It is known,for example, to react ethane with hydrogen chloride and oxygen in contact with catalysts which include copper oxides, copper ~ chlorides, copper oxychlorides, copper silicates and the like .~ ,.~
to produce chlorinated hydrocarbons such as vinyl chloride, ~ ethyl chloride, ethylene dichloride and the like. The yields - of any desired specific chlorinated products, however, have been generally poor which has led to a search for active catalysts to .~ .
give cleaner or more selective reactions. One such catalyst is described in U.S.patent 3,173,962. This patent teaches the oxy-chlorination of an alkane having from 2 to 6 carbon atoms and preferably ethane in the presence of an iron phosphate prefer-ably supported on an inert carrier such as silica, for example.
Other metallic cations such as nickel, cobalt, copper, chromium, - tin, lead, cerium, manganese, bismuth, magnesium, cadmium, vana-dium and generally metals of Groups I through IV of the Peri-odic Table are disclosed as useful in conjunction with iron.
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fD -2-4~4 . .
The products obtained with this catalyst are predominantly ethylene, ethyl chloride and sometimes 1,2-dichloroethane (DCE), - also called ethylene dichloride.
In another patent Br. 1,039,369, the conversion of ethane to vinyl chloride by oxychlorination in the presence of water is disclosed using as catalysts inorganic oxygen-containing compounds such as simple oxides and oxychlorides of ~` multivalent metals such as iron, cerium, manganese, uranium, vanadium, nickel, chromium and cobalt together with promoters which are inorganic compounds of Li, Na, K, Pb, Ce, Ca, Mg, ` Sr, Ba, Zn, Cd, B, In, P and Tl. The catalysts can be initial-ly introduced in the form of oxygenated compounds such as car-bonates, nitrates, phosphates and hydroxides and thus it is dis-` closed inorganic compounds resulting from this form of intro-; 15 duction may also be present in the reaction zone. Even with the preferred iron-containing catalysts, and steam as a reac-tant, however, the selectivity of conversion of ethane to vinyl chloride in a single-step reaction does not generally average 50%.
::
Other catalytic compositions disclosed as useful for converting ethane directly to vinyl chloride are described in -U.S. patents 3,420,901 and 3,557,229. In the former patent, a complex copper-alumina catalyst is employed in the oxychlorina-tion reaction but there is no indication of the effectiveness of the catalyst for producing vinyl chloride from ethane. There are no examples directed to the use of ethane as a reactant to support the bare disclosure. In the latter patent, a catalyst melt formed from a chloride of a multivalent metal, such as copper chloride, is employed but only 37% of the ethane con-verted goes to the production of chlorinated hydrocarbons in-cluding vinyl chloride which constituted only 18.8% of the 45~
chlorinated products mixture.
It is evident from the foregoing consideration of the prior art, that the known processes for producing vinyl chloride from ethane in one step suffer from the obvious disadvantage that the known catalysts for the reaction are not highly selective.
It is, accordingly, an object of the present invention in this ; embodiment to provide an oxychlorination process utilizing a novel catalyst to produce vinyl chloride in high yields in one step from ethane. This and other objects and advantages of the invention will become more readily apparent from the following detailed description of this embodiment of the invention.
According to the broader embodiments of the present invention, monohalogenated olefins are selectively prepared in high yields by reacting an alkane having 2 to 4 carbon atoms, un-.::
saturated hydrocarbons or hal~oalkanes having 2-6 carbon atoms ~` and at least 2 hydrogen atoms on adjacent carbon atoms with a hydrogen halide and a source of oxygen at a temperature in the range from about 200C to about 700C in contact with a cata-lyst system comprising a copper halide and an alkali metal phos-phate deposited or carried on an inorganic support. More parti-cularly, one aspect of the above broader embodiments of the present invention is directed to the production of vinyl chlor-ide by the oxychlorination of ethane at a temperature from about 400C to 650C, or more specifically from about 500C to about 600 C in contact with a catalyst comprising copper chloride and potassium phosphate; a further aspect of this invention involves reacting an olefin with the same catalyst at a temperature of from 200 to 650C or more specifically 400 to 600C ; or a still further aspect involves the dehydrogenation of a haloalkane having from 2 to 6 carbon atoms and at least two hydrogen atoms on adjacent carbon atoms with the same catalyst at a temperature of from 400 to 700C. The catalyst may contain other components D _4_ .
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such as halides of the platinum-group metals, e.g., platinum itself, palladium, ruthenium, rhodium, iridium and the like, and the halides of the metals of Groups I and II of the periodic system.
The catalyst employed in the various processes of the -invention is readily prepared by admixing of the support material or carrier with a solution of the copper halide or of the copper ,:
halide and any other metal halides which are to be included in the catalyst composition in the proper amount in water or, pre-ferably, in an alcohol. After thorough mixing, the solids are separated from the mixture or slurry either mechanically and/or by evaporation of the solvent and then subjected to drying at a ; temperature from about 100C to about 200 C for a period of from ~ about one to about ten hours. The solid remaining is converted :.,.
into any desired form by grinding, pelletizing etc., after which . .
it is heat-treated while under fluidization conditions with air ` at a temperature from about 300 to about 600C for a period of from about 2 to about 8 hours and preferably at a temperature of about 450C for about 3 to about 6 hours.
The heat-treated material is then contacted with an aqueous solution in the desired concentration of the alkali met-al phosphate, dried and again heat-treated under conditions sub-stantially the same as those described above to obtain the fin-ished catalyst. Alternatively, the alkali metal phosphate can be incorporated by adding it to the dried copper-containing solid before the initial heat treatment is carried out.
Where more than two metal compounds are used in the catalyst composition, the compounds of the metals other than copper can be deposited on the support as described above. The resulting solid is then mixed with anhydrous cupric chloride and again heat-treated with air at 450C for 6 hours to provide .,~' .
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the finished catalyst. When alkali metal compounds such as sodium and potassium chlorides, for example, are used in the catalyst composition, these are placed on the support first using the usual impregnation, drying and calcining technique ~; 5 because they tend to precipitate platinum and sometimes copper from the solution.
Various materials may serve as suitable supports for .: .
the catalyst of the present invention. Among the many which can be used may be mentioned alumina, silica gel, silica-alumina, silica-magnesia, bauxite, magnesia, silicon carbide, titania, zirconium silicate and the like. The preferred support is alum-ina. The surface area of the support may range up to 150 m2/g but catalyst supports having a low surface area, i.e.,~30 m /g , are preferred and those of~10 m2/g are even more preferred.
: : , ~ ~ 15 Available support materials of high surface area may be readily ~ .
calcined to reduce their surface area to the desired level.
The concentration of copper on the support may vary from about 0.1 to about 10% by weight and preferably is from , about 1 to about 5% by weight. The concentration of alkali metal as the phosphate is from about 1% by wt. to about 10% by wt. and preferably is from about 3 to about 6% by weight. Com-pounds of so-called platinum-group metals can also be incor-porated in the catalyst composition. These are compounds of such metals as platinum, palladium, rhodium, ruthenium, osmium, and iridium, particularly the halide of these metals, which may have a beneficial effect on the reaction. When a platinum-group ; metal is employed with the copper, the concentration of this metal is generally in the range from about 0.1% by weight to - about 1% by weight and preferably is about 0.5% by weight. Al-kali metal halides may also be incorporated if desired in the catalyst composition. The amounts of the latter if they areused will generally vary between about 0.5 to about 5.0% by ` weight.
In the one embodiment of the invention using an alkane reactant, the present process is particularly appli-cable to the manufacture of monochlorinated and monobromin-ated substituted olefins such as vinyl chloride and vinyl bromide from ethane. However, other alkanes such as propane and butane can be oxychlorinated employing the catalyst of the invention to produce the corresponding monohalogenated olefins.
The hydrogen halide employed is that corresponding to the desired monohalogenated olefin to be produced. Thus, when vinyl chloride is produced according to the invention, hydrogen chloride is employed as the hydrogen halide while for vinyl bro-mide as a product, hydrogen bromide is employed.
Elemental oxygen may be used or any oxygen-containing gas stream such as air. Gaseous inert diluents such as nitrogen, helium, carbon dioxide and the like or excess ethane or excess hydrogen chloride may also be present but are not necessary.
In the case of the process using the alkane reactant, the reiative molar proportions of alkane, olefin or haloalkane, hydrogen halide and oxygen may vary from 0.25 to 3.0 moles of ; oxygen per mole of reactant and from 0.5 to 5 moles of hydro-gen halide per mole of reactant. Preferred molar ratios include 0.5 - 1.5 mole of oxygen and 0.5 to 2 moles of hydrogen halide per mole of reactant.
Generally, for the various processes the reaction is conducted at a temperature from about 200C to about 700 C but preferably reaction temperature are readily ascertained. Suit-able pressures are those in the range from atmospheric to about 7.0 Kg/cm2. Preferably, pressure is maintained at approximately atmospherie.
The various processes may be eonducted using either a fixed bed, moving bed or fluidized bed of catalyst but the use of the fluidized bed technique is preferred. The reactants ~' 5 may be eharged to the bottom of the reactor containing the catalyst in a finely divided state thus serving to fluidize , the catalyst. The three reactants may be introduced into the :
, reactor in separate streams or the air or oxygen may be intro-duced into a mixture of the reactant and hydrogen halide.
Because of the explosive limits of the various hydroearbon feeds, care should be taken not to allow a mixture of a reac-- tant and oxygen to reach reaction temperature in the absence of the hydrogen halide. The minimum gas velocity for fluidizing the catalyst is low. Linear gas velocities of the order of 3.0 to 15.2 cm per second are generally satisfaetory and avoid exeessive earryover of eatalyst fines. The depth of the eata--- lyst bed should be sueh as to permit a satisfactory fluidized condition of the eatalyst to be aehieved and to provide suffi-;~ eient eontaet time for substantial eonversion to the desired produet at the temperature employed. A superficial contact , time of 0.1 to 10 seconds or more is sufficient under the usual operating conditions with a preferred contact time being in the range from about 1 to about 5 seconds.
The process of the invention using an alkane reactant is illustrated in the following examples which are not, however, to be construed as limiting the scope thereof in any manner except as it is limited in the attached claims.
Conversions and yields given inthe tables are defined as follows:
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.
% Conversion = HCl in Cfeted x 100 % Yield = x convertedttd product x 100 .,:
where x = C2H6 or HCl ~ .
A catalyst containing 3.0% copper, 0.5% lithium, 0.5%
platinum and 3% potassium as potassium phosphate supported on alumina and having a surface area of 7.6 m2/g was prepared as follows. To a solution of 0.5494 g of the hexahydrate of hydrochloroplatinic acid (H2PtC16 6 H2O), 1.2241 g of lithium chloride (LiCl) and 2.5614 g of copper chloride (CuC12) in 50 ml of methanol there was added with thorough mixing 40 g of - alumina known by the trademark "Alcoa F-l" of Aluminum Company of America, which had been calcined at 1100C to provide a surface area of 9.4 m2/g. The resulting mixture was subjected to evaporation and dried at 110C for about 2 hours. It was then transferred to a fluidized bed reactor and fluidized with nitrogen at 400C for 6 hours. After the heat-treatment ;~ .
the solid material was added to a solution of 2.1683 g of ~ 20 K3PO4 in 30 ml of H2O and mixed thoroughly. The liquid was ;~ evaporated from the mixture after which it was fluidized with air at 400C for three hours.
The above-described catalyst was employed in a fluid-ized bed for the reaction between ethane, hydrogen chloride and air. The reaction was carired out in a pyrex reactor, one inch in diameter and 24 inches long equipped with rotameters for measuring gas flow, flow regulators and pressure controllers.
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The reactor was equipped with Nichrome heating tape and as-bestos insulation. Reactor temperature was measured by means of thermocouples located at five different points in the ther-mowell from the bottom tc the top of the reactor. The gaseous reactants were introduced at a rate sufficient to fluidize the catalyst. Catalyst fines carried out by the reaction effluent leaving the top of the reactor were accumulated in a collector heated by an electric tape to a temperature from i400 to 150C
to prevent condensation to liquid product. The effluent gases were then passed through suitable condensers and water and liquid product were collected in suitable receivers. Off-gas was sent through a hydrogen chloride scrubber and then vented. Un-reacted HCl was collected in water and titrated using a stan-dard alkali solution. Product composition was determined by gas chromatographic analysis of an off-gas sample taken from a sampling valve located ahead of the HCl scrubber. Results of two runs at a contact time of 1.0 second, two different reac-, tant mole ratios and a temperature of 550C are presented inTable 1 below showing the two major products of the reaction, vinyl chloride (VCM) and ethyl chloride (EtCl). Minor amounts of other chlorinated hydrocarbons such as tetrachloroethylene, trichloroethylene, 1,1- and 1,2-dichloroethane, chloroform, and other saturated and unsaturated halohydrocarbons were also identified in the product.
Run No. 1 2 C2H6HCl/air, mol 1/1/4.76 1/1/7.15 HCl Conversion, % 62.8 77.5 VCM Yield, mol%
on C~H6 77.1 76.9 on HCl 62.7 60.3 EtCl Yield, mol %
on C~H6 11.1 10.7 on HCl 9 3-4 ~ -10-,C~ 4 2 0 - l 9 - 0 6 3 9A
:, . .
It will be seen that the yields of vinyl chloride resulting from the use of this catalyst containing K3PO4 are significantly better than those obtained in the prior art for a single-step reaction.
In addition the major by-product is ethyl chloride which can be subsequently oxydehydrogenated to vinyl chloride by simple recycle operations using the same catalyst employed herein as described in my copending application filed of even date herewith.
EX~IPLE 2 A copper chloride catalyst containing potassium phos-phate was prepared as follows: About 710 g of the same alumina employed in Example 1 was calcined to reduce its surface area to below 10 m2/g. The calcined alumina was placed in two Vycor dishes in a muffle furnace at 1200C for about 16 hours. The final surface area of the alumina was found to be about 3.1 m2/g.
To the alumina there was added with stirring 45 g of ~- CuC12 dissolved in 630 ml of methanol. The mixture was dried ' under fluidized bed conditions with air flow at room temperature until it became a free-flowing solid. The solid was dried at 110C overnight and then heat-treated at 450C while fluidized ~ 20 with air for about 6 hours. The dried material was cooled to ; room temperature and 115 g of K3PO4 dissolved in 200 ml of water was added to it. The resulting mixture after thorough mixing was dried in a fluidized bed at 450C. The finished catalyst contained 3.0% copper and 9% potassium as X3PO4 and had a sur-face area of 1.2 m2/g.
The catalyst prepared as described above was charged - to the reactor described in Example 1. Ethane, HCl and air were introduced into the bottom of the reactor at rates to maintain the catalyst in a fluidized state and the reaction products were withdrawn from the top and treated as described in Example 1.
Conditions of reaction and the results obtained are recorded in : `
-: ' Table 2. The selectivity of the copper and potassium phosphate-containing catalyst is readily apparent from the high yields of vinyl chloride which can be obtained under the optimum conditions.
As in Example 1, the other major product of the reaction is ethyl chloride which can be subsequently recycled to increase the vinyl chloride yield because the catalyst is also suitable for con-version of ethyl chloride to vinyl chloride by oxydehydrogena-tion.
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PREPARATION OF VINYL CHLORIDE
The present application relates, in one embodiment, to the conversion of alkanes to unsaturated halogenated products such as vinyl halides. More particularly, in that embodiment, it relates to the conversion of ethane directly to vinyl chlor-ide in high yields by the oxychlorination reaction utilizing a highly selective catalyst.
The conversion of hydrocarbons unsaturated hydro-carbons or haloalkanes to useful halogenated hydrocarbons by the so-called "oxychlorination" reaction, i.e., the reaction of ` the hydrocarbon, a hydrogen halide as the source of the halogen and a source of elemental oxygen, in the presence of copper con-; taining catalysts is well known in the art. It is known,for example, to react ethane with hydrogen chloride and oxygen in contact with catalysts which include copper oxides, copper ~ chlorides, copper oxychlorides, copper silicates and the like .~ ,.~
to produce chlorinated hydrocarbons such as vinyl chloride, ~ ethyl chloride, ethylene dichloride and the like. The yields - of any desired specific chlorinated products, however, have been generally poor which has led to a search for active catalysts to .~ .
give cleaner or more selective reactions. One such catalyst is described in U.S.patent 3,173,962. This patent teaches the oxy-chlorination of an alkane having from 2 to 6 carbon atoms and preferably ethane in the presence of an iron phosphate prefer-ably supported on an inert carrier such as silica, for example.
Other metallic cations such as nickel, cobalt, copper, chromium, - tin, lead, cerium, manganese, bismuth, magnesium, cadmium, vana-dium and generally metals of Groups I through IV of the Peri-odic Table are disclosed as useful in conjunction with iron.
'' .
fD -2-4~4 . .
The products obtained with this catalyst are predominantly ethylene, ethyl chloride and sometimes 1,2-dichloroethane (DCE), - also called ethylene dichloride.
In another patent Br. 1,039,369, the conversion of ethane to vinyl chloride by oxychlorination in the presence of water is disclosed using as catalysts inorganic oxygen-containing compounds such as simple oxides and oxychlorides of ~` multivalent metals such as iron, cerium, manganese, uranium, vanadium, nickel, chromium and cobalt together with promoters which are inorganic compounds of Li, Na, K, Pb, Ce, Ca, Mg, ` Sr, Ba, Zn, Cd, B, In, P and Tl. The catalysts can be initial-ly introduced in the form of oxygenated compounds such as car-bonates, nitrates, phosphates and hydroxides and thus it is dis-` closed inorganic compounds resulting from this form of intro-; 15 duction may also be present in the reaction zone. Even with the preferred iron-containing catalysts, and steam as a reac-tant, however, the selectivity of conversion of ethane to vinyl chloride in a single-step reaction does not generally average 50%.
::
Other catalytic compositions disclosed as useful for converting ethane directly to vinyl chloride are described in -U.S. patents 3,420,901 and 3,557,229. In the former patent, a complex copper-alumina catalyst is employed in the oxychlorina-tion reaction but there is no indication of the effectiveness of the catalyst for producing vinyl chloride from ethane. There are no examples directed to the use of ethane as a reactant to support the bare disclosure. In the latter patent, a catalyst melt formed from a chloride of a multivalent metal, such as copper chloride, is employed but only 37% of the ethane con-verted goes to the production of chlorinated hydrocarbons in-cluding vinyl chloride which constituted only 18.8% of the 45~
chlorinated products mixture.
It is evident from the foregoing consideration of the prior art, that the known processes for producing vinyl chloride from ethane in one step suffer from the obvious disadvantage that the known catalysts for the reaction are not highly selective.
It is, accordingly, an object of the present invention in this ; embodiment to provide an oxychlorination process utilizing a novel catalyst to produce vinyl chloride in high yields in one step from ethane. This and other objects and advantages of the invention will become more readily apparent from the following detailed description of this embodiment of the invention.
According to the broader embodiments of the present invention, monohalogenated olefins are selectively prepared in high yields by reacting an alkane having 2 to 4 carbon atoms, un-.::
saturated hydrocarbons or hal~oalkanes having 2-6 carbon atoms ~` and at least 2 hydrogen atoms on adjacent carbon atoms with a hydrogen halide and a source of oxygen at a temperature in the range from about 200C to about 700C in contact with a cata-lyst system comprising a copper halide and an alkali metal phos-phate deposited or carried on an inorganic support. More parti-cularly, one aspect of the above broader embodiments of the present invention is directed to the production of vinyl chlor-ide by the oxychlorination of ethane at a temperature from about 400C to 650C, or more specifically from about 500C to about 600 C in contact with a catalyst comprising copper chloride and potassium phosphate; a further aspect of this invention involves reacting an olefin with the same catalyst at a temperature of from 200 to 650C or more specifically 400 to 600C ; or a still further aspect involves the dehydrogenation of a haloalkane having from 2 to 6 carbon atoms and at least two hydrogen atoms on adjacent carbon atoms with the same catalyst at a temperature of from 400 to 700C. The catalyst may contain other components D _4_ .
~".
such as halides of the platinum-group metals, e.g., platinum itself, palladium, ruthenium, rhodium, iridium and the like, and the halides of the metals of Groups I and II of the periodic system.
The catalyst employed in the various processes of the -invention is readily prepared by admixing of the support material or carrier with a solution of the copper halide or of the copper ,:
halide and any other metal halides which are to be included in the catalyst composition in the proper amount in water or, pre-ferably, in an alcohol. After thorough mixing, the solids are separated from the mixture or slurry either mechanically and/or by evaporation of the solvent and then subjected to drying at a ; temperature from about 100C to about 200 C for a period of from ~ about one to about ten hours. The solid remaining is converted :.,.
into any desired form by grinding, pelletizing etc., after which . .
it is heat-treated while under fluidization conditions with air ` at a temperature from about 300 to about 600C for a period of from about 2 to about 8 hours and preferably at a temperature of about 450C for about 3 to about 6 hours.
The heat-treated material is then contacted with an aqueous solution in the desired concentration of the alkali met-al phosphate, dried and again heat-treated under conditions sub-stantially the same as those described above to obtain the fin-ished catalyst. Alternatively, the alkali metal phosphate can be incorporated by adding it to the dried copper-containing solid before the initial heat treatment is carried out.
Where more than two metal compounds are used in the catalyst composition, the compounds of the metals other than copper can be deposited on the support as described above. The resulting solid is then mixed with anhydrous cupric chloride and again heat-treated with air at 450C for 6 hours to provide .,~' .
D
, -5~
the finished catalyst. When alkali metal compounds such as sodium and potassium chlorides, for example, are used in the catalyst composition, these are placed on the support first using the usual impregnation, drying and calcining technique ~; 5 because they tend to precipitate platinum and sometimes copper from the solution.
Various materials may serve as suitable supports for .: .
the catalyst of the present invention. Among the many which can be used may be mentioned alumina, silica gel, silica-alumina, silica-magnesia, bauxite, magnesia, silicon carbide, titania, zirconium silicate and the like. The preferred support is alum-ina. The surface area of the support may range up to 150 m2/g but catalyst supports having a low surface area, i.e.,~30 m /g , are preferred and those of~10 m2/g are even more preferred.
: : , ~ ~ 15 Available support materials of high surface area may be readily ~ .
calcined to reduce their surface area to the desired level.
The concentration of copper on the support may vary from about 0.1 to about 10% by weight and preferably is from , about 1 to about 5% by weight. The concentration of alkali metal as the phosphate is from about 1% by wt. to about 10% by wt. and preferably is from about 3 to about 6% by weight. Com-pounds of so-called platinum-group metals can also be incor-porated in the catalyst composition. These are compounds of such metals as platinum, palladium, rhodium, ruthenium, osmium, and iridium, particularly the halide of these metals, which may have a beneficial effect on the reaction. When a platinum-group ; metal is employed with the copper, the concentration of this metal is generally in the range from about 0.1% by weight to - about 1% by weight and preferably is about 0.5% by weight. Al-kali metal halides may also be incorporated if desired in the catalyst composition. The amounts of the latter if they areused will generally vary between about 0.5 to about 5.0% by ` weight.
In the one embodiment of the invention using an alkane reactant, the present process is particularly appli-cable to the manufacture of monochlorinated and monobromin-ated substituted olefins such as vinyl chloride and vinyl bromide from ethane. However, other alkanes such as propane and butane can be oxychlorinated employing the catalyst of the invention to produce the corresponding monohalogenated olefins.
The hydrogen halide employed is that corresponding to the desired monohalogenated olefin to be produced. Thus, when vinyl chloride is produced according to the invention, hydrogen chloride is employed as the hydrogen halide while for vinyl bro-mide as a product, hydrogen bromide is employed.
Elemental oxygen may be used or any oxygen-containing gas stream such as air. Gaseous inert diluents such as nitrogen, helium, carbon dioxide and the like or excess ethane or excess hydrogen chloride may also be present but are not necessary.
In the case of the process using the alkane reactant, the reiative molar proportions of alkane, olefin or haloalkane, hydrogen halide and oxygen may vary from 0.25 to 3.0 moles of ; oxygen per mole of reactant and from 0.5 to 5 moles of hydro-gen halide per mole of reactant. Preferred molar ratios include 0.5 - 1.5 mole of oxygen and 0.5 to 2 moles of hydrogen halide per mole of reactant.
Generally, for the various processes the reaction is conducted at a temperature from about 200C to about 700 C but preferably reaction temperature are readily ascertained. Suit-able pressures are those in the range from atmospheric to about 7.0 Kg/cm2. Preferably, pressure is maintained at approximately atmospherie.
The various processes may be eonducted using either a fixed bed, moving bed or fluidized bed of catalyst but the use of the fluidized bed technique is preferred. The reactants ~' 5 may be eharged to the bottom of the reactor containing the catalyst in a finely divided state thus serving to fluidize , the catalyst. The three reactants may be introduced into the :
, reactor in separate streams or the air or oxygen may be intro-duced into a mixture of the reactant and hydrogen halide.
Because of the explosive limits of the various hydroearbon feeds, care should be taken not to allow a mixture of a reac-- tant and oxygen to reach reaction temperature in the absence of the hydrogen halide. The minimum gas velocity for fluidizing the catalyst is low. Linear gas velocities of the order of 3.0 to 15.2 cm per second are generally satisfaetory and avoid exeessive earryover of eatalyst fines. The depth of the eata--- lyst bed should be sueh as to permit a satisfactory fluidized condition of the eatalyst to be aehieved and to provide suffi-;~ eient eontaet time for substantial eonversion to the desired produet at the temperature employed. A superficial contact , time of 0.1 to 10 seconds or more is sufficient under the usual operating conditions with a preferred contact time being in the range from about 1 to about 5 seconds.
The process of the invention using an alkane reactant is illustrated in the following examples which are not, however, to be construed as limiting the scope thereof in any manner except as it is limited in the attached claims.
Conversions and yields given inthe tables are defined as follows:
.,~
`- D -8-'' '.
.
% Conversion = HCl in Cfeted x 100 % Yield = x convertedttd product x 100 .,:
where x = C2H6 or HCl ~ .
A catalyst containing 3.0% copper, 0.5% lithium, 0.5%
platinum and 3% potassium as potassium phosphate supported on alumina and having a surface area of 7.6 m2/g was prepared as follows. To a solution of 0.5494 g of the hexahydrate of hydrochloroplatinic acid (H2PtC16 6 H2O), 1.2241 g of lithium chloride (LiCl) and 2.5614 g of copper chloride (CuC12) in 50 ml of methanol there was added with thorough mixing 40 g of - alumina known by the trademark "Alcoa F-l" of Aluminum Company of America, which had been calcined at 1100C to provide a surface area of 9.4 m2/g. The resulting mixture was subjected to evaporation and dried at 110C for about 2 hours. It was then transferred to a fluidized bed reactor and fluidized with nitrogen at 400C for 6 hours. After the heat-treatment ;~ .
the solid material was added to a solution of 2.1683 g of ~ 20 K3PO4 in 30 ml of H2O and mixed thoroughly. The liquid was ;~ evaporated from the mixture after which it was fluidized with air at 400C for three hours.
The above-described catalyst was employed in a fluid-ized bed for the reaction between ethane, hydrogen chloride and air. The reaction was carired out in a pyrex reactor, one inch in diameter and 24 inches long equipped with rotameters for measuring gas flow, flow regulators and pressure controllers.
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The reactor was equipped with Nichrome heating tape and as-bestos insulation. Reactor temperature was measured by means of thermocouples located at five different points in the ther-mowell from the bottom tc the top of the reactor. The gaseous reactants were introduced at a rate sufficient to fluidize the catalyst. Catalyst fines carried out by the reaction effluent leaving the top of the reactor were accumulated in a collector heated by an electric tape to a temperature from i400 to 150C
to prevent condensation to liquid product. The effluent gases were then passed through suitable condensers and water and liquid product were collected in suitable receivers. Off-gas was sent through a hydrogen chloride scrubber and then vented. Un-reacted HCl was collected in water and titrated using a stan-dard alkali solution. Product composition was determined by gas chromatographic analysis of an off-gas sample taken from a sampling valve located ahead of the HCl scrubber. Results of two runs at a contact time of 1.0 second, two different reac-, tant mole ratios and a temperature of 550C are presented inTable 1 below showing the two major products of the reaction, vinyl chloride (VCM) and ethyl chloride (EtCl). Minor amounts of other chlorinated hydrocarbons such as tetrachloroethylene, trichloroethylene, 1,1- and 1,2-dichloroethane, chloroform, and other saturated and unsaturated halohydrocarbons were also identified in the product.
Run No. 1 2 C2H6HCl/air, mol 1/1/4.76 1/1/7.15 HCl Conversion, % 62.8 77.5 VCM Yield, mol%
on C~H6 77.1 76.9 on HCl 62.7 60.3 EtCl Yield, mol %
on C~H6 11.1 10.7 on HCl 9 3-4 ~ -10-,C~ 4 2 0 - l 9 - 0 6 3 9A
:, . .
It will be seen that the yields of vinyl chloride resulting from the use of this catalyst containing K3PO4 are significantly better than those obtained in the prior art for a single-step reaction.
In addition the major by-product is ethyl chloride which can be subsequently oxydehydrogenated to vinyl chloride by simple recycle operations using the same catalyst employed herein as described in my copending application filed of even date herewith.
EX~IPLE 2 A copper chloride catalyst containing potassium phos-phate was prepared as follows: About 710 g of the same alumina employed in Example 1 was calcined to reduce its surface area to below 10 m2/g. The calcined alumina was placed in two Vycor dishes in a muffle furnace at 1200C for about 16 hours. The final surface area of the alumina was found to be about 3.1 m2/g.
To the alumina there was added with stirring 45 g of ~- CuC12 dissolved in 630 ml of methanol. The mixture was dried ' under fluidized bed conditions with air flow at room temperature until it became a free-flowing solid. The solid was dried at 110C overnight and then heat-treated at 450C while fluidized ~ 20 with air for about 6 hours. The dried material was cooled to ; room temperature and 115 g of K3PO4 dissolved in 200 ml of water was added to it. The resulting mixture after thorough mixing was dried in a fluidized bed at 450C. The finished catalyst contained 3.0% copper and 9% potassium as X3PO4 and had a sur-face area of 1.2 m2/g.
The catalyst prepared as described above was charged - to the reactor described in Example 1. Ethane, HCl and air were introduced into the bottom of the reactor at rates to maintain the catalyst in a fluidized state and the reaction products were withdrawn from the top and treated as described in Example 1.
Conditions of reaction and the results obtained are recorded in : `
-: ' Table 2. The selectivity of the copper and potassium phosphate-containing catalyst is readily apparent from the high yields of vinyl chloride which can be obtained under the optimum conditions.
As in Example 1, the other major product of the reaction is ethyl chloride which can be subsequently recycled to increase the vinyl chloride yield because the catalyst is also suitable for con-version of ethyl chloride to vinyl chloride by oxydehydrogena-tion.
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EXA~IPLE 3 ' _ An oxychlorination catalyst was prepared as follows.
About 100 cc (41.89 gm) of an inorganic support identified by -~ the trademark for silica and perlite products "Celite" of , 5 Johns-Mansville Corporation (Type V) having a particle size , of 30-80 mesh and a surface area of 3.1 m2/g was impregnated with a solution of 5.3023 g of CuC12 in 70 ml of methanol.
The mixture was subjected to evaporation, dried and then `: heat-treated during fluidization at 450C for 6 hours. To ~: .
the resulting solid there was added a solution of 6.8124 g of K3PO4 in 70 ml of water. After drying, the material was heat-treated under fluidization conditions at 450C for 3 hours. The finished catalyst contained 6.0% copper and 9.0 potassium as K3PO4 and had a surface area of 1.7 m2/g.
-, The catalyst prepared as described above was used ;~ to oxychlorinate ethane in the apparatus of Example 1 and ,-,,~, i , following the procedure described in that example. Conditions '~ of reaction and the results obtained are presented in Table
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EXA~IPLE 3 ' _ An oxychlorination catalyst was prepared as follows.
About 100 cc (41.89 gm) of an inorganic support identified by -~ the trademark for silica and perlite products "Celite" of , 5 Johns-Mansville Corporation (Type V) having a particle size , of 30-80 mesh and a surface area of 3.1 m2/g was impregnated with a solution of 5.3023 g of CuC12 in 70 ml of methanol.
The mixture was subjected to evaporation, dried and then `: heat-treated during fluidization at 450C for 6 hours. To ~: .
the resulting solid there was added a solution of 6.8124 g of K3PO4 in 70 ml of water. After drying, the material was heat-treated under fluidization conditions at 450C for 3 hours. The finished catalyst contained 6.0% copper and 9.0 potassium as K3PO4 and had a surface area of 1.7 m2/g.
-, The catalyst prepared as described above was used ;~ to oxychlorinate ethane in the apparatus of Example 1 and ,-,,~, i , following the procedure described in that example. Conditions '~ of reaction and the results obtained are presented in Table
3 below.
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As outlined previously, the present invention is ; applicable to the manufacture of monochlorinated and monobrom- -; inated substituted olefins using an olefin reactant, and in this embodiment, the process is mainly directed to the pre-paration of vinyl chloride. The olefins which may be employed as starting materials include ethylene, propylene, straight-and branched-chain olefins con~ining 4 or more carbon atoms, diolefins, cyclic olefins such as cyclohexene and olefins con-taining aromatic groups such as benzene and styrene.
The hydrogen halide in this olefin reactant process employed is that corresponding to the desired monohalogenated - olefin to be produced. Thus, when vinyl chloride is produced .i according to the invention, hydrogen chloride is employed as ; the hydrogen halide while for vinyl bromide as a product, hydrogen bromide is employed. Also, elemental oxygen may be ;: ~
used or any oxygen-containing gas stream such as air. Gaseous , .
`i inert diluents such as nitrogen, helium, carbon dioxide and the ~; like or excess ethylene or excess hydrogen halide may also be present but are not necessary.
. ~ ".
: 20 The relative molar proportions of olefin, hydrogen ~ halide and oxygen may vary from 0.25 to 2.0 moles of oxygen per ; mole of olefin and from 0.5 to 5 moles of hydrogen halide per mole of olefin. Preferred molar ratios include 0.5 - l.0 mole of oxygen and 0.5 to 2 moles of hydrogen halide per mole of olefin.
; Generally, the reaction involving the olefin is con-ducted at a temperature from about 200C to about 650C but pre-ferably reaction temperatures are maintained in the range from about 400-600C. Suitable pressures are those in the range ~ 30 from atmospheric to about 100 psig. Preferably, pressure is - maintained at approximately atmospheric.
The process using the olefin reactant may be 1~ 54 conducted- using either a fixed bed or fluidized bed of catalyst but the use of the fluidized bed technique is preferred. Thus, in the process using the olefin, the reactants may be eharged to the bottom of the reactor containing the eatalyst in a finely divided state thus serving to fluidize the eatalyst. The three reaetants may be introdueed into the reaetor in separate streams or the air or oxygen may be introdueed into a mixture of the olefin and hydrogen halide. Beeause of the explosive limits of the various hydroearbon feeds, eare should be taken not to allow a mixture of olefin and oxygen to reach reaction temperature in the absenee of the hydrogen halide. The minimum gas veloeity for fluidizing the catalyst is low. Linear gas veloeities of the order of 3.0 to 15.2 em per seeond are gener-ally satisfaetory and avoid exeessive carryover of catalyst fines. The depth of the catalyst bed should be sueh as to per-mit a satisfactory fluidized condition of the catalyst to be achieved and to provide sufficient contact time for substantial conversion to the desired produet at the temperature employed.
A superficial contaet time of 0.1 to 10 seeonds or more is sufficient under the usual operating conditions with a preferred ~;~ 20 contact time being in the range from about 1 to about 5 seconds.
The process using the olefin reactant is illustrated in the following examples which are not, however, to be constru-ed as limiting the scope thereof in any manner except as it is limited in the attached elaims. Conversions and yields given in the tables are defined as follows:
% Convention = HC1 inaCfeted x lO0 on x = x eonvertedttd product x lO0 where x 2 4 . .
f~54 :
.
Several catalysts were prepared as follows:
A. Approximately 40.3 g of alumina supplied commercially by Alumina Co. of America and known to the trade as "Alcoa F-l"
alumina having a particle size of about 50-100 mesh was treated with hot air at 1150C for 64 hr to provide alumina having a : .
surface area of 12.4 m2/g. The alumina was then impregnated with a solution of 2.56 g of CuC12 in 35 ml of methanol. The mixture was subjected to evaporation, dried and heat-treated .; under fluidization conditions at 450C with nitrogen for 3 hours , .
and with air for 3 hours. The finished catalyst contained 3.0%
copper and had a surface area of about 10 m2/g.
B. To Catalyst A prepared as described above was added ; a solution of about 2.2 g of K3PO4 dissolved in 35 ml of water.
The catalyst was dried and heat-treated at 450C with air for ~. . , 3 hours. This catalyst as analyzed contained 3.0~ copper and 3.0% potassium as K3PO4.
C. To Catalyst A prepared as described above was added a solution of 4.4 g of K3PO4 in 35 ml of water. The catalyst was then dried and heat-treated at 450C for about 3 hours. The resulting catalyst having a surface area of 4.0 m2/g contained 3.0% copper and 9.0% K as K3PO4.
^;~ Catalysts A, B and C described above were employed in ;~ a fluidized bed for the reaction between ethylene, hydrogen chloride and air in molar proportions of 1:0.5:2.4 at temperatures from 450 to 550C. The reaction was carried out in a pyrex reactor, 2.54 cm in diameter and 61.0 cm in length, equipped with rota-meters for measuring gas flow, flow regulators and pressure controllers. The reactor was wrapped with Nichrome heating tape and asbestos insulation. Reactor temperature was measured ' by means of thermocouples located at five different points in the thermowell from the bottom to the top of the reactor and controlled by a temperature controller. The gaseous reactants were introduced at the bottom of the reactor at a rate sufficient to fluidize the catalyst : ethylene, 14.2 liters/hr, HCl 7.1 liters/hr and air at 34.0/liters/hr. Catalyst fines carried out by the reaction effluent leaving the top of the reactor were . .
accumulated in a collector which was heated by an electric tape to a temperature from 140-150C to prevent condensation of liquid product. The effluent gases were then passed through suitable condensers and water and liquid product were collected in suit-. able receivers. Off-gas was sent to a hydrogen chloride scrub-ber and then vented. Unreacted HCl was collected in water and titrated using a standard alkali solution. Product composition was determined by gas chromatographic analysis of an off-gas ~; sample taken from the sampling valve located ahead of the HCl scrubber. Results with the three different catalysts are pre-sented in Table 4 below showing the two chlorinated products - predominating in the reaction products. Very minor amounts of other chlorinated hydrocarbons such as dichloroethylene, tri-chloroethylene, and other chlorinated saturated and unsaturated ` hydrocarbons were also identified in the product. It will be - seen that the copper chloride catalysts treated with K3PO4 are significantly more selectivs to the monohalogenated com-pound, vinyl chloride, when higher temperatures are employed.
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C~TALYST A CATALYST B CATALYST C
.
Temperature, C 450 500 450 500 550 500 550 Contact Time, sec. 1.36 1.28 1.36 1.28 1.20 1.28 1.20 HCl Conversion, % 84.1 63.8 97.4 95.1 84.3 96.5 94.0 ;~ ~ Yield, mol ~
on C2H4 44.5 74.2 34.5 68.7 82.3 62.1 83.6 on HCl 28.9 61.0 21.2 54.2 75.5 46.4 77.3 ~; 1,2-DCE Yield,m~l~
~i~ 10 on C2H4 52.2 20.5 58.3 25.1 8.1 31.8 7.5 on HCl 67.8 32.7 71.6 38.6 14.9 46.5 13.4 ; ~inyl Chloride -~ 2 1,2-Dichlorceth~ne EXAMPLE S
. . - .
A catalyst, designated Catalyst D, containing 3.0~ Cu, 1.5% K and 0.5% Pt supported on alumina of the same type employed - in Example 3 was prepared by adding 40.0 g of the alumina which ` had been heated in air at 450C for 3 hours to a solution of - 1.0252 g of KOH in 50 ml of water. The mixture was subjected to evaporation and dried at 110C for 2 hours after which it was calcined at 1150C for 15 hours. The calcined solid was then impregnated with a solution of 0.5297 g of the hexahydrate of hydrochloroplatinic acid (H2PtC12 6 H20) and 2.5402 g of CuC12 (anhydrous) in 50 ml of methanol. The resulting mixture was dried and heat-treated with nitrogen at 400C for 6 hours.
A second catalyst, designated Catalyst E, was prepared by impregnating 40 g of alumina from the same source as used in Example 3 with a solution of 0.5239 g of H2PtC16 6H20 and 2.5391 g of anhydrous CuC12 in 50 ml of methanol. The mixture was ~' ,~,, ; evaporated to dryness and was treated with nitrogen in a flu-- idized reactor at 400C for 4 hours. It was then reduced with hydrogen at 400C for 4 hours. To the resulting solid was added a solution of 1.0101 g of KOH in 50 ml of water followed by thorough mixing. After drying at 110C for 2 hours, the catalyst was calcined at 1100C for 16 hours. The finished catalyst con-tained 3.0% Cu, 1.5~ K and 0.5~ Pt and had a surface area of 13.8 ' To a portion of Catalyst D there was added a solution of 1.1034 g K3PO4 in 40 ml of water. After thorough mixing, the resulting mixture was dried, and heat-treated with nitrogen at 400C for 4 hours. This catalyst was designated Catalyst F.
; Catalyst F was calcined at 1100C for 16 hours to pro-vide the catalyst designated Catalyst G.
Each of Catalysts D, E, F and G were employed for re-acting ethylene, HCl and 2 in the same apparatus and under the same conditions given in Example 3 except that temperatures ranged from 400C to 500C. Results of these runs are presented in Table 5 below.
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As outlined previously, the present invention is ; applicable to the manufacture of monochlorinated and monobrom- -; inated substituted olefins using an olefin reactant, and in this embodiment, the process is mainly directed to the pre-paration of vinyl chloride. The olefins which may be employed as starting materials include ethylene, propylene, straight-and branched-chain olefins con~ining 4 or more carbon atoms, diolefins, cyclic olefins such as cyclohexene and olefins con-taining aromatic groups such as benzene and styrene.
The hydrogen halide in this olefin reactant process employed is that corresponding to the desired monohalogenated - olefin to be produced. Thus, when vinyl chloride is produced .i according to the invention, hydrogen chloride is employed as ; the hydrogen halide while for vinyl bromide as a product, hydrogen bromide is employed. Also, elemental oxygen may be ;: ~
used or any oxygen-containing gas stream such as air. Gaseous , .
`i inert diluents such as nitrogen, helium, carbon dioxide and the ~; like or excess ethylene or excess hydrogen halide may also be present but are not necessary.
. ~ ".
: 20 The relative molar proportions of olefin, hydrogen ~ halide and oxygen may vary from 0.25 to 2.0 moles of oxygen per ; mole of olefin and from 0.5 to 5 moles of hydrogen halide per mole of olefin. Preferred molar ratios include 0.5 - l.0 mole of oxygen and 0.5 to 2 moles of hydrogen halide per mole of olefin.
; Generally, the reaction involving the olefin is con-ducted at a temperature from about 200C to about 650C but pre-ferably reaction temperatures are maintained in the range from about 400-600C. Suitable pressures are those in the range ~ 30 from atmospheric to about 100 psig. Preferably, pressure is - maintained at approximately atmospheric.
The process using the olefin reactant may be 1~ 54 conducted- using either a fixed bed or fluidized bed of catalyst but the use of the fluidized bed technique is preferred. Thus, in the process using the olefin, the reactants may be eharged to the bottom of the reactor containing the eatalyst in a finely divided state thus serving to fluidize the eatalyst. The three reaetants may be introdueed into the reaetor in separate streams or the air or oxygen may be introdueed into a mixture of the olefin and hydrogen halide. Beeause of the explosive limits of the various hydroearbon feeds, eare should be taken not to allow a mixture of olefin and oxygen to reach reaction temperature in the absenee of the hydrogen halide. The minimum gas veloeity for fluidizing the catalyst is low. Linear gas veloeities of the order of 3.0 to 15.2 em per seeond are gener-ally satisfaetory and avoid exeessive carryover of catalyst fines. The depth of the catalyst bed should be sueh as to per-mit a satisfactory fluidized condition of the catalyst to be achieved and to provide sufficient contact time for substantial conversion to the desired produet at the temperature employed.
A superficial contaet time of 0.1 to 10 seeonds or more is sufficient under the usual operating conditions with a preferred ~;~ 20 contact time being in the range from about 1 to about 5 seconds.
The process using the olefin reactant is illustrated in the following examples which are not, however, to be constru-ed as limiting the scope thereof in any manner except as it is limited in the attached elaims. Conversions and yields given in the tables are defined as follows:
% Convention = HC1 inaCfeted x lO0 on x = x eonvertedttd product x lO0 where x 2 4 . .
f~54 :
.
Several catalysts were prepared as follows:
A. Approximately 40.3 g of alumina supplied commercially by Alumina Co. of America and known to the trade as "Alcoa F-l"
alumina having a particle size of about 50-100 mesh was treated with hot air at 1150C for 64 hr to provide alumina having a : .
surface area of 12.4 m2/g. The alumina was then impregnated with a solution of 2.56 g of CuC12 in 35 ml of methanol. The mixture was subjected to evaporation, dried and heat-treated .; under fluidization conditions at 450C with nitrogen for 3 hours , .
and with air for 3 hours. The finished catalyst contained 3.0%
copper and had a surface area of about 10 m2/g.
B. To Catalyst A prepared as described above was added ; a solution of about 2.2 g of K3PO4 dissolved in 35 ml of water.
The catalyst was dried and heat-treated at 450C with air for ~. . , 3 hours. This catalyst as analyzed contained 3.0~ copper and 3.0% potassium as K3PO4.
C. To Catalyst A prepared as described above was added a solution of 4.4 g of K3PO4 in 35 ml of water. The catalyst was then dried and heat-treated at 450C for about 3 hours. The resulting catalyst having a surface area of 4.0 m2/g contained 3.0% copper and 9.0% K as K3PO4.
^;~ Catalysts A, B and C described above were employed in ;~ a fluidized bed for the reaction between ethylene, hydrogen chloride and air in molar proportions of 1:0.5:2.4 at temperatures from 450 to 550C. The reaction was carried out in a pyrex reactor, 2.54 cm in diameter and 61.0 cm in length, equipped with rota-meters for measuring gas flow, flow regulators and pressure controllers. The reactor was wrapped with Nichrome heating tape and asbestos insulation. Reactor temperature was measured ' by means of thermocouples located at five different points in the thermowell from the bottom to the top of the reactor and controlled by a temperature controller. The gaseous reactants were introduced at the bottom of the reactor at a rate sufficient to fluidize the catalyst : ethylene, 14.2 liters/hr, HCl 7.1 liters/hr and air at 34.0/liters/hr. Catalyst fines carried out by the reaction effluent leaving the top of the reactor were . .
accumulated in a collector which was heated by an electric tape to a temperature from 140-150C to prevent condensation of liquid product. The effluent gases were then passed through suitable condensers and water and liquid product were collected in suit-. able receivers. Off-gas was sent to a hydrogen chloride scrub-ber and then vented. Unreacted HCl was collected in water and titrated using a standard alkali solution. Product composition was determined by gas chromatographic analysis of an off-gas ~; sample taken from the sampling valve located ahead of the HCl scrubber. Results with the three different catalysts are pre-sented in Table 4 below showing the two chlorinated products - predominating in the reaction products. Very minor amounts of other chlorinated hydrocarbons such as dichloroethylene, tri-chloroethylene, and other chlorinated saturated and unsaturated ` hydrocarbons were also identified in the product. It will be - seen that the copper chloride catalysts treated with K3PO4 are significantly more selectivs to the monohalogenated com-pound, vinyl chloride, when higher temperatures are employed.
,, --19--., :
':
., .
C~TALYST A CATALYST B CATALYST C
.
Temperature, C 450 500 450 500 550 500 550 Contact Time, sec. 1.36 1.28 1.36 1.28 1.20 1.28 1.20 HCl Conversion, % 84.1 63.8 97.4 95.1 84.3 96.5 94.0 ;~ ~ Yield, mol ~
on C2H4 44.5 74.2 34.5 68.7 82.3 62.1 83.6 on HCl 28.9 61.0 21.2 54.2 75.5 46.4 77.3 ~; 1,2-DCE Yield,m~l~
~i~ 10 on C2H4 52.2 20.5 58.3 25.1 8.1 31.8 7.5 on HCl 67.8 32.7 71.6 38.6 14.9 46.5 13.4 ; ~inyl Chloride -~ 2 1,2-Dichlorceth~ne EXAMPLE S
. . - .
A catalyst, designated Catalyst D, containing 3.0~ Cu, 1.5% K and 0.5% Pt supported on alumina of the same type employed - in Example 3 was prepared by adding 40.0 g of the alumina which ` had been heated in air at 450C for 3 hours to a solution of - 1.0252 g of KOH in 50 ml of water. The mixture was subjected to evaporation and dried at 110C for 2 hours after which it was calcined at 1150C for 15 hours. The calcined solid was then impregnated with a solution of 0.5297 g of the hexahydrate of hydrochloroplatinic acid (H2PtC12 6 H20) and 2.5402 g of CuC12 (anhydrous) in 50 ml of methanol. The resulting mixture was dried and heat-treated with nitrogen at 400C for 6 hours.
A second catalyst, designated Catalyst E, was prepared by impregnating 40 g of alumina from the same source as used in Example 3 with a solution of 0.5239 g of H2PtC16 6H20 and 2.5391 g of anhydrous CuC12 in 50 ml of methanol. The mixture was ~' ,~,, ; evaporated to dryness and was treated with nitrogen in a flu-- idized reactor at 400C for 4 hours. It was then reduced with hydrogen at 400C for 4 hours. To the resulting solid was added a solution of 1.0101 g of KOH in 50 ml of water followed by thorough mixing. After drying at 110C for 2 hours, the catalyst was calcined at 1100C for 16 hours. The finished catalyst con-tained 3.0% Cu, 1.5~ K and 0.5~ Pt and had a surface area of 13.8 ' To a portion of Catalyst D there was added a solution of 1.1034 g K3PO4 in 40 ml of water. After thorough mixing, the resulting mixture was dried, and heat-treated with nitrogen at 400C for 4 hours. This catalyst was designated Catalyst F.
; Catalyst F was calcined at 1100C for 16 hours to pro-vide the catalyst designated Catalyst G.
Each of Catalysts D, E, F and G were employed for re-acting ethylene, HCl and 2 in the same apparatus and under the same conditions given in Example 3 except that temperatures ranged from 400C to 500C. Results of these runs are presented in Table 5 below.
' .
111~454 20-19-0639A
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4~4 The efficacious effect of K3PO4 as compared to potas-sium added in some other form is evident from the increased selectivities to the production of vinyl chloride demonstrated by Catalysts F and G as compared to Catalysts D and E.
` S EXAMPLE 6 A series of runs was made in which ethylene was reacted with HCl and 2 to produce vinyl chloride employing a copper chloride catalyst containing K3PO4. The catalyst was prepared by first calcining 710 g of the same alumina as used in the pre-vious examples to reduce the surface area to below 10 m2/g. The calcined alumina was placed in 2 Vycor dishes in a muffle furnace at 1200C for about 16 hours. The final surface area of the alumina was found to be 3.1 m2/g when it was removed after this time.
To the alumina there was added 45 g of CuC12 dissolved in 630 ml of methanol. This mixture was dried under fluidized bed conditions with air flow at room temperature until it be-came a free-flowing solid. The solid was dried at 110C over-night and then heat treated at 450C while fluidized with air for about 6 hours. The dried material was cooled to room tem-perature and 115 g of K3PO4 dissolved in 200 ml of water was added to it. The resulting mixture after thorough mixing was dried in a fluidized ~ed at 450C. The finished catalyst con-tained 3.0% copper, 9% potassium as K3PO4 and had a surface area of 1.2 m2/g.
About 50 cc (53.9 g) Oc this catalyst was charged to the reactor described in Example 1. Ethylene, HC1 and air were introduced into the bottom of the reactor to maintain . . .
the catalyst in a fluidized state and reaction products were withdrawn from the top and treated as described in Example 3.
::-. .
,, 4~4 , , Conditions of reaction and the results obtained are recorded in Table 6. The selectivity of the copper and potassium phos-` phate-containing catalystis readily apparent from the highyields . of vinyl chloride o~tained under the varying conditions em-ployed.
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` S EXAMPLE 6 A series of runs was made in which ethylene was reacted with HCl and 2 to produce vinyl chloride employing a copper chloride catalyst containing K3PO4. The catalyst was prepared by first calcining 710 g of the same alumina as used in the pre-vious examples to reduce the surface area to below 10 m2/g. The calcined alumina was placed in 2 Vycor dishes in a muffle furnace at 1200C for about 16 hours. The final surface area of the alumina was found to be 3.1 m2/g when it was removed after this time.
To the alumina there was added 45 g of CuC12 dissolved in 630 ml of methanol. This mixture was dried under fluidized bed conditions with air flow at room temperature until it be-came a free-flowing solid. The solid was dried at 110C over-night and then heat treated at 450C while fluidized with air for about 6 hours. The dried material was cooled to room tem-perature and 115 g of K3PO4 dissolved in 200 ml of water was added to it. The resulting mixture after thorough mixing was dried in a fluidized ~ed at 450C. The finished catalyst con-tained 3.0% copper, 9% potassium as K3PO4 and had a surface area of 1.2 m2/g.
About 50 cc (53.9 g) Oc this catalyst was charged to the reactor described in Example 1. Ethylene, HC1 and air were introduced into the bottom of the reactor to maintain . . .
the catalyst in a fluidized state and reaction products were withdrawn from the top and treated as described in Example 3.
::-. .
,, 4~4 , , Conditions of reaction and the results obtained are recorded in Table 6. The selectivity of the copper and potassium phos-` phate-containing catalystis readily apparent from the highyields . of vinyl chloride o~tained under the varying conditions em-ployed.
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5~L
In another process the present invention is particu-; larly applicable in the manufacture of monochlorinated and mono-brominated olefins from the corresponding alkyl halides which contain at least one hydrogen atom on adjacent carbon atoms and - 5 2 to 6 carbon atoms. It has particular utility in providing vinyl chloride in good yield from ethyl chloride but is also ; useful, for example, for producing allyl chloride from propyl ::
chloride, vinyl bromide from ethyl bromide, vinyl dichloride from ethyl dichloride, 3-chlorobutene-1 from butyl chloride, .
10 2-chlorobutene from 2-chlorobutane as well as butadiene from both, and the like.
In this process elemental oxygen is supplied to the reaction either pure or diluted with inert gases such as nitrogen, helium, carbon dioxide and the like or as air.
15 Excess haloalkane may be employed if desired but is not neces-sary. The realtive molar proportions of haloalkane and oxygen are generally in the range from about 1:0.25 to about 1:2 and ~ -preferably from about 1:0.5 to about 1:1 in the preferred temperature range.
The above process involves a reaction which can be conducted at temperatures from about ~00 to about 700C but : preferably reaction temperatures are maintained in the tempera-:
ture range from 500 to 600C. Suitable pressures are those in the range from atmospheric to about 100 psig. Preferably, 25 pressure is maintained at approximately atmospheric.
The above process may be conducted using either a fixed bed, a moving bed, or a fluidized bed of catalyst but the fluid-ized bed technique is preferred. The reactants may be charged to the bottom of the reactor containing the catalyst in a finely di-30 vided state thus serving to fluidize the catalyst. The minimum gas velocity for fluidizing the catalyst is low. Linear gas vel-ocities of the order of 0.1 to 0.5 foot per second are ; 20-19-0639A
generally satisfactory and avoid excessive carryover of `~ catalyst fines. The depth of the catalyst bed should be such as to permit a satisfactory fluidized condition of the catalyst to be achieved and to provide sufficient contact time for sub-S stantial conversion to the desired product at the temperature employed.
The residence or contact time of the reactants in the reaction zone under any given set of reaction conditions de-- pends upon all of the factors involved in the reaction. Contact times ranging from about 0.1 to about 5 to 10 or 15 seconds are satisfactory, Preferably, contact times are maintained in the range from about 1 to about 5 seconds. Conversions and yields given in the tables are defined as follows:
: `
%EtCllConversion = EtCl rienaCfeeed x 100 %VCM Yield = VCM produced x 100 EtCl reacted EtCl = Ethyl chloride VCM = Vinyl chloride A catalyst containing 3.0~ copper, 0.5% lithium,0.5%
platinum and 3% potassium as potassium phosphate having asurface area of 7.4 m2/g was prepared as follows. To a solution of 0.5494 g of the hexahydrate of hydrochloroplatinic acid (H2PtC16 6 H2O), 1.2241 g of lithium chloride (LiCl) and 2.5614 g of copper chloride (CuC12) in 50 ml of methanol there '~ was added with thorough mixing 40 g of alumina known by the trade name "Alcoa F-l" which had been calcined at 1100C to provide a surface area of 9.4 m2/g. The resulting mixture was subjected to evaporation and dried at 110C for about 2 hours.
4~4 It was then transferred to a fluidized bed reactor and flu-idized with nitrogen at 400C for 6 hours. After the heat-treatment, the solid material was added to a solution of ~ 2.1683 g of K3PO4 in 30 ml of H20 and mixed thoroughly. The : 5 liquid was evaporated from the mixture after which it was flu-idized with air at 400C for three hours.
A series of runs were made in which ethyl chloride was dehydrogenated in the presence of oxygen using the above-described catalyst. About 20 ml (22 g) of the catalyst was charged to a pyrex reactor, one inch in diameter and 24 inches long, equipped with rotameters for measuring gas flow, flow regulations and pressure controllers. The reactor was equipped - with Nichrome heating tape and asbestos insulation. Reactor temperature was measured by means of thermocouples located at five different points in the thermowell from the bottom to the top of the reactor. The catalyst was maintained in a fluidized condition by introduction of the gaseous reactants at the bot-., tom of the reactor. Catalyst fines carried out by the reactor were accumulated in a collector heated by an electric tape to a temperature from 140 to 150C to prevent condensation to liquid product. The effluent gases were then passed through suitable condensers and water and liquid product were collected in suit-- able receivers. Off-gas was sent through a hydrogen chloride scrubber and then vented. Unreacted HCl was collected in water and titrated using a standard alkali solution. Product compo-sition was determined by gas chromatographic analysis of an off-gas sample ta'.~en from a sampling valve located ahead of the HCl scrubber. Conditions of reaction and the results obtained in the runs are presented in Table 7.
~ 4S~ 20-19-0639A
Run Temp. Contact C H Cl/AirC2H5Cl VCM
No. C Time, Sec. (~o~es) Conv., % Yield,%
1 600 0.44 1/4.76 79.7 S9.2 `~ s 2 550 0.47 1/4.76 65.1 59.3 3 500 1.0 1/4.76 67.3 58.4 ` 4 550 0.95 1/4.76 86.7 68.2 400 1.15 1/4.76 14.3 24.1 ~ 6 450 1.07 1/4.76 30.4 42 -~ lO 7 600 0.89 1/4.76 95.9 70.9 8 500 2.0 1/4.76 84.3 67.4 9 500 0.5 1/4.76 60.5 52.7 500 1.0 1/7.15 68.3 55.3 ` 11 500 1.0 1/9.5 69.2 47.8 12 500 l .0 1/2.38 61.8 69 '',:' ~XAMPLE 8 Ethyl chloride was dehydrogonated in tho prosenco of . .
oxygen using a catalyst containing copper and potassium phos-phate supported on alumina. The catalyst was prepared as fol-.... j lows.
Approximately 40. 3 g of aluraina supplied commercially - by Aluminum Co. of America and known to the trade as "Alcoa F-l"
alumina having a particle size of about 50-lO0 mesh was treated :~ with hot air at 1150C for 64 hours to provide alumina having a surface area of 12. 4 m2/g. The alumina was then impregnated with a solution of 2. 56 g of CuCl2 in 35 ml of methanol. The . .
~ 20-19-0639A
:,.
~ 459t . , mixture was subjected to evaporation, dried and heat-treated under fluidization conditions at 45QC with nitrogen for 3 hours and with air for 3 hours.
After heat treatment there was added to the mixture a solution of 4.4 g of K3PO4 in 35 ml of water. The resulting mixture was then dried and heat-treated under fluidization conditions at 450C for about three hours. The finished catalyst '! ;' had a surface area of 4.0 m2/g and contained 3.0% copper and .: , .
~; 9.0~ potassium as K3PO4.
The reaction was carried out in the same apparatus and following the same procedure given in Example 7 above. Reaction conditions and results are presented in Table 8 below.
Run Temp. Contact C H Cl/Air C H5Cl VCM
No. C Time, Sec. (~o~es) Conv., ~ Yield,%
1 500 1.73 1/4.76 79 49.9 , 2 550 1.64 1/4.76 91.1 63.6 ,,, .. -~
....
.
In another process the present invention is particu-; larly applicable in the manufacture of monochlorinated and mono-brominated olefins from the corresponding alkyl halides which contain at least one hydrogen atom on adjacent carbon atoms and - 5 2 to 6 carbon atoms. It has particular utility in providing vinyl chloride in good yield from ethyl chloride but is also ; useful, for example, for producing allyl chloride from propyl ::
chloride, vinyl bromide from ethyl bromide, vinyl dichloride from ethyl dichloride, 3-chlorobutene-1 from butyl chloride, .
10 2-chlorobutene from 2-chlorobutane as well as butadiene from both, and the like.
In this process elemental oxygen is supplied to the reaction either pure or diluted with inert gases such as nitrogen, helium, carbon dioxide and the like or as air.
15 Excess haloalkane may be employed if desired but is not neces-sary. The realtive molar proportions of haloalkane and oxygen are generally in the range from about 1:0.25 to about 1:2 and ~ -preferably from about 1:0.5 to about 1:1 in the preferred temperature range.
The above process involves a reaction which can be conducted at temperatures from about ~00 to about 700C but : preferably reaction temperatures are maintained in the tempera-:
ture range from 500 to 600C. Suitable pressures are those in the range from atmospheric to about 100 psig. Preferably, 25 pressure is maintained at approximately atmospheric.
The above process may be conducted using either a fixed bed, a moving bed, or a fluidized bed of catalyst but the fluid-ized bed technique is preferred. The reactants may be charged to the bottom of the reactor containing the catalyst in a finely di-30 vided state thus serving to fluidize the catalyst. The minimum gas velocity for fluidizing the catalyst is low. Linear gas vel-ocities of the order of 0.1 to 0.5 foot per second are ; 20-19-0639A
generally satisfactory and avoid excessive carryover of `~ catalyst fines. The depth of the catalyst bed should be such as to permit a satisfactory fluidized condition of the catalyst to be achieved and to provide sufficient contact time for sub-S stantial conversion to the desired product at the temperature employed.
The residence or contact time of the reactants in the reaction zone under any given set of reaction conditions de-- pends upon all of the factors involved in the reaction. Contact times ranging from about 0.1 to about 5 to 10 or 15 seconds are satisfactory, Preferably, contact times are maintained in the range from about 1 to about 5 seconds. Conversions and yields given in the tables are defined as follows:
: `
%EtCllConversion = EtCl rienaCfeeed x 100 %VCM Yield = VCM produced x 100 EtCl reacted EtCl = Ethyl chloride VCM = Vinyl chloride A catalyst containing 3.0~ copper, 0.5% lithium,0.5%
platinum and 3% potassium as potassium phosphate having asurface area of 7.4 m2/g was prepared as follows. To a solution of 0.5494 g of the hexahydrate of hydrochloroplatinic acid (H2PtC16 6 H2O), 1.2241 g of lithium chloride (LiCl) and 2.5614 g of copper chloride (CuC12) in 50 ml of methanol there '~ was added with thorough mixing 40 g of alumina known by the trade name "Alcoa F-l" which had been calcined at 1100C to provide a surface area of 9.4 m2/g. The resulting mixture was subjected to evaporation and dried at 110C for about 2 hours.
4~4 It was then transferred to a fluidized bed reactor and flu-idized with nitrogen at 400C for 6 hours. After the heat-treatment, the solid material was added to a solution of ~ 2.1683 g of K3PO4 in 30 ml of H20 and mixed thoroughly. The : 5 liquid was evaporated from the mixture after which it was flu-idized with air at 400C for three hours.
A series of runs were made in which ethyl chloride was dehydrogenated in the presence of oxygen using the above-described catalyst. About 20 ml (22 g) of the catalyst was charged to a pyrex reactor, one inch in diameter and 24 inches long, equipped with rotameters for measuring gas flow, flow regulations and pressure controllers. The reactor was equipped - with Nichrome heating tape and asbestos insulation. Reactor temperature was measured by means of thermocouples located at five different points in the thermowell from the bottom to the top of the reactor. The catalyst was maintained in a fluidized condition by introduction of the gaseous reactants at the bot-., tom of the reactor. Catalyst fines carried out by the reactor were accumulated in a collector heated by an electric tape to a temperature from 140 to 150C to prevent condensation to liquid product. The effluent gases were then passed through suitable condensers and water and liquid product were collected in suit-- able receivers. Off-gas was sent through a hydrogen chloride scrubber and then vented. Unreacted HCl was collected in water and titrated using a standard alkali solution. Product compo-sition was determined by gas chromatographic analysis of an off-gas sample ta'.~en from a sampling valve located ahead of the HCl scrubber. Conditions of reaction and the results obtained in the runs are presented in Table 7.
~ 4S~ 20-19-0639A
Run Temp. Contact C H Cl/AirC2H5Cl VCM
No. C Time, Sec. (~o~es) Conv., % Yield,%
1 600 0.44 1/4.76 79.7 S9.2 `~ s 2 550 0.47 1/4.76 65.1 59.3 3 500 1.0 1/4.76 67.3 58.4 ` 4 550 0.95 1/4.76 86.7 68.2 400 1.15 1/4.76 14.3 24.1 ~ 6 450 1.07 1/4.76 30.4 42 -~ lO 7 600 0.89 1/4.76 95.9 70.9 8 500 2.0 1/4.76 84.3 67.4 9 500 0.5 1/4.76 60.5 52.7 500 1.0 1/7.15 68.3 55.3 ` 11 500 1.0 1/9.5 69.2 47.8 12 500 l .0 1/2.38 61.8 69 '',:' ~XAMPLE 8 Ethyl chloride was dehydrogonated in tho prosenco of . .
oxygen using a catalyst containing copper and potassium phos-phate supported on alumina. The catalyst was prepared as fol-.... j lows.
Approximately 40. 3 g of aluraina supplied commercially - by Aluminum Co. of America and known to the trade as "Alcoa F-l"
alumina having a particle size of about 50-lO0 mesh was treated :~ with hot air at 1150C for 64 hours to provide alumina having a surface area of 12. 4 m2/g. The alumina was then impregnated with a solution of 2. 56 g of CuCl2 in 35 ml of methanol. The . .
~ 20-19-0639A
:,.
~ 459t . , mixture was subjected to evaporation, dried and heat-treated under fluidization conditions at 45QC with nitrogen for 3 hours and with air for 3 hours.
After heat treatment there was added to the mixture a solution of 4.4 g of K3PO4 in 35 ml of water. The resulting mixture was then dried and heat-treated under fluidization conditions at 450C for about three hours. The finished catalyst '! ;' had a surface area of 4.0 m2/g and contained 3.0% copper and .: , .
~; 9.0~ potassium as K3PO4.
The reaction was carried out in the same apparatus and following the same procedure given in Example 7 above. Reaction conditions and results are presented in Table 8 below.
Run Temp. Contact C H Cl/Air C H5Cl VCM
No. C Time, Sec. (~o~es) Conv., ~ Yield,%
1 500 1.73 1/4.76 79 49.9 , 2 550 1.64 1/4.76 91.1 63.6 ,,, .. -~
....
.
Claims (40)
1. A process for producing monohalogenated olefins utilizing a reactant, a hydrogen halide, a source of oxygen, a temperature of 200 to 700°C and a catalyst comprising a copper halide and an alkali metal phosphate deposited upon an inorganic support, characterized wherein said reactant is an alkane having from 2 to 4 carbon atoms, unsaturated hydrocarbons or haloalkanes having from 2 to 6 carbon atoms and at least two hydrogen atoms on adjacent carbon atoms.
2. A process according to claim 1 characterized in that said reactant is ethane and said temperature is from 400 to 650°C.
3. A process according to claim 1 characterized wherein said catalyst copper halide is cupric chloride and said catalyst alkali metal phosphate is potassium phosphate.
4. A process according to claim 2 characterized wherein said catalyst copper halide is cupric chloride and said catalyst alkali metal phosphate is potassium phosphate.
5. A process according to claim 1 characterized wherein the inorganic support is alumina and the concentration of copper on said support is from 1 to 10 percent by weight, the concentration of potassium is from 1 to 10 percent by weight and said surface area of said catalyst is less than 10m2/gram.
6. A process according to claim 3 characterized wherein the inorganic support is alumina and the concentration of copper on said support is from 1 to 10 percent by weight, the concentra-tion of potassium is from 1 to 10 percent by weight and said sur-face area of said catalyst is less than 10m2/gram.
7. A process according to claim 4 characterized wherein the inorganic support is alumina and the concentration of copper on said support is from 1 to 10 percent by weight, the concen-tration of potassium is from 1 to 10 percent by weight and said surface area of said catalyst is less than 10m2/gram.
8. A process according to claims 1, 3 or 4 characterized in that said catalysts also contain from 0.1 to 1% by weight of a platinum group metal.
9. A process according to claims 5, 6 or 7 characterized in that said catalyst also contain from 0.1 to 1% by weight of a platinum group metal.
10. A process as defined in claim 1, which comprises re-acting an alkane having 2 to 4 carbon atoms with a hydrogen halide and a source of oxygen at a temperature in the range from about 400°C. to about 650°C. in contact with a catalyst consist-ing essentially of a copper halide and an alkali metal phosphate and from about 0.1% to about 1% by weight of a platinum group metal, deposited upon an inorganic support.
11. A process as defined in claim 10, which comprises reacting ethane with hydrogen chloride and a source of oxygen at a temperature in the range from about 400°C. to about 650°C.
in contact with a catalyst consisting essentially of a copper halide and an alkali metal phosphate and from about 0.1%
to about 1% by weight of a platinum group metal, deposited upon an inorganic support, to thereby form vinyl chloride.
in contact with a catalyst consisting essentially of a copper halide and an alkali metal phosphate and from about 0.1%
to about 1% by weight of a platinum group metal, deposited upon an inorganic support, to thereby form vinyl chloride.
12. The process of claim 10 or 11 wherein said inorganic support is alumina.
13. The process of claim 10 or 11 wherein said copper halide is cupric chloride and said alkali metal phosphate is potassium phosphate.
14. The process of claim 10 or 11 wherein said copper halide is cupric chloride and said alkali metal phosphate is potassium phosphate, and wherein the concentration of copper on said support is from about 0.1 to about 10% by weight and the concentration of potassium as the phosphate is from about 1% to about 10% by weight.
15. The process of claim 10 or 11 wherein said copper halide is cupric chloride and said alkali metal phosphate is potassium phosphate, and wherein the concentration of copper on said support is from about 0.1 to about 10% by weight and the concentration of potassium as the phosphate is from about 1% to about 10% by weight, and wherein said catalyst has a surface area of <10m2/g.
16. The process of claim 10 or 11 wherein said copper halide is cupric chloride and said alkali metal phosphate is potassium phosphate, and wherein the concentration of copper on said support is from about 0.1 to about 10% by weight and the concentration of potassium as the phosphate is from about 1% to about 10% by weight, and wherein said catalyst has a surface area of <10m2/g., and wherein said temperature is in the range from about 500 to about 600°C.
17. The process of claim 10 or 11 wherein said copper halide is cupric chloride and said alkali metal phosphate is potassium phosphate, and wherein the concentration of copper on said support is from about 0.1 to about 10% by weight and the concentration of potassium as the phosphate is from about 1% to about 10% by weight, and wherein said catalyst has a surface area of <10m2/g., and wherein said temperature is in the range from about 500 to about 600°C., and wherein the relative molar proportions of alkane to hydrogen halide to oxygen are in the range from 1:0.25:0.5 to 1:2:5.
18. The process of claim 10 or 11 wherein said copper halide is cupric chloride and said alkali metal phosphate is potassium phosphate, and wherein the concentration of copper on said support is from about 0.1 to about 10% by weight and the concentration of potassium as the phosphate is from about 1% to about 10% by weight, and wherein said catalyst has a surface area of<10m2/g., and wherein said temperature is in the range from about 500 to about 600°C., and wherein the relative molar proportions of alkane to hydrogen halide to oxygen are in the range from 1:0.25:0.5 to 1:2:5, and wherein said platinum-group metal is platinum.
19. The process of claim 10 or 11 wherein said copper halide is cupric chloride and said alkali metal phosphate is potassium phosphate, and wherein the concentration of copper on said support is from about 0.1 to about 10% by weight and the concentration of potassium as the phosphate is from about 1% to about 10% by weight, and wherein said catalyst has a surface area of < 10m2/g., and wherein said temperature is in the range from about 500 to about 600°C., and wherein the relative molar proportions of alkane to hydrogen halide to oxygen are in the range from 1:0.25:0.5 to 1:2:5, and wherein said platinum-group metal is platinum, and wherein said catalyst also contains from about 0.5 to about 5.0% by weight of an alkali metal chloride.
20. A process as defined in claim 1 which comprises reacting an olefin with a hydrogen halide and a source of oxygen at a temperature in the range from about 200°C. to about 650°C. in contact with a catalyst consisting essentially of a copper halide and an alkali metal phosphate deposited on an inorganic support.
21. The process of claim 20 wherein said inorganic support is alumina.
22. The process of claim 21 wherein said olefin is ethylene and said hydrogen halide is hydrogen chloride.
23. The process of claim 22 wherein said copper halide is cupric chloride and said alkali metal phosphate is potassium phosphate.
24. The process of claim 23 wherein said concentration of copper on said support is from about 0.1 to about 10% by weight and the concentration of potassium as potassium phosphate is from about 1% to about 10% by weight.
25. The process of claim 24 wherein said catalyst has a surface area of <10m2/g.
26. The process of claim 25 wherein said olefin is reacted with a hydrogen halide and the reaction temperature is in the range from about 400° to about 600°C.
27. The process of claim 26 wherein the molar proportions of ethylene, hydrogen chloride and oxygen are in the range from about 1:0.25:0.5 to about 1:2:5.
28. The process of claim 27 wherein said catalyst also contains from about 0.5 to about 5.0% by weight of an alkali metal chloride.
29. A process as defined in claim 20 which comprises reacting an olefin with a hydrogen halide and a source of oxygen at a temperature in the range from about 200°C. to about 650°C. in contact with a catalyst consisting essentially of a copper halide and an alkali metal phosphate and from about 0.1% to about 1% by weight of platinum deposited on an inorganic support.
30. A process as defined in claim 1 which comprises dehydrogenating in the presence of oxygen and a hydrogen halide, a haloalkane containing 2 to 6 carbon atoms and at least two hydrogen atoms on adjacent carbon atoms at a temperature in the range from about 400° to about 700°C.
in contact with a catalyst comprising a halide of copper and an alkali metal phosphate on an inorganic support.
in contact with a catalyst comprising a halide of copper and an alkali metal phosphate on an inorganic support.
31. The process of claim 30 wherein said support is alumina.
32. The process of claim 31 wherein said haloalkane is ethyl chloride.
33. The process of claim 32 wherein said copper halide is cupric chloride and said alkali metal phosphate is potassium phosphate.
34. The process of claim 33 wherein the concentration of copper in said catalyst is from about 0.1 to about 10% by weight and the concentration of potassium as the phosphate is from about 1% to about 10% by weight.
35. The process of claim 34 wherein said catalyst has a surface area of <10m2/g.
36. The process of claim 35 wherein said temperature is in the range from about 500°C. to about 600°C.
37. The process of claim 36 wherein the molar proportions of ethyl chloride to oxygen are in the range from about 1:0.25 to about 1:2.
38. The process of claim 37 wherein said catalyst also contains from about 0.1 to about 1% by weight of a platinum-group metal.
39. The process of claim 38 wherein said platinum-group metal is platinum.
40. The process of claim 38 or 39 wherein said catalyst also contains from about 0.5 to about 2.0% by weight of an alkali metal chloride.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US85689077A | 1977-12-02 | 1977-12-02 | |
| US856,889 | 1977-12-02 | ||
| US856,890 | 1977-12-02 | ||
| US05/856,889 US4300005A (en) | 1977-12-02 | 1977-12-02 | Preparation of vinyl chloride |
| US856,840 | 1977-12-02 | ||
| US05/856,840 US4302617A (en) | 1977-12-02 | 1977-12-02 | Conversion of ethyl chloride to vinyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1111454A true CA1111454A (en) | 1981-10-27 |
Family
ID=27420385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA317,242A Expired CA1111454A (en) | 1977-12-02 | 1978-12-01 | Preparation of vinyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1111454A (en) |
-
1978
- 1978-12-01 CA CA317,242A patent/CA1111454A/en not_active Expired
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