CA2010314A1 - Process and catalyst for hydrochlorination of hydrocarbons - Google Patents
Process and catalyst for hydrochlorination of hydrocarbonsInfo
- Publication number
- CA2010314A1 CA2010314A1 CA002010314A CA2010314A CA2010314A1 CA 2010314 A1 CA2010314 A1 CA 2010314A1 CA 002010314 A CA002010314 A CA 002010314A CA 2010314 A CA2010314 A CA 2010314A CA 2010314 A1 CA2010314 A1 CA 2010314A1
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- CA
- Canada
- Prior art keywords
- cation
- catalyst
- group
- potassium
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Methyl chloride is produced by contacting methanol and hydrogen chloride in the vapor phase in the presence of KZnCl3 supported on silica. The process produces methyl chloride in good yield with minimal formation of dimethyl ether as a by-product
Description
2~,03~.4 - -PROCESS AND CATALYST
FOR HYDROCHLORINATION OF HYDROCARBONS
This invention relate_ to catalytio hydro- ;
chlorination processes. In particular, the invention relates to the catalytic hydrochlorination of hydro-carbyl compounds.
: Chlorinated hydrocarbons have various utilities .:- a~ lndustrial chemicals and solvents. For example, methyl chloride i8 useful aq a catalyst carrier in low temperature polymerizations; as a fluid for thermometric and thermo~tatic equipment; as a methylating agent in organlc synthesis, such as of methylcellulose; in the preparation of silicone rubberq; and as an extractant and low temperature solvent.
Method~ for the production of chlorinated ~;: hydrocarbons, such as methyl chloride, are well-known.
In a typical method for the production of methyl chlo-ride, vaporized methanol and hydrogen chloride are mixed in approximately equimolar proportions and pa~ed through a converter packed with a catalyst such as alumina gel or zinc chloride on activated carbon to form - methyl chloride. Other known methods involve reactions : 25 in the liquid phaqe uqing an aqueou~ solution of , :
~ ~
~ 36~467-F -1-h::
2~ 3~4 catalyst. For example, U.S. Patent 4,073,816 teaches that monochloroalkane~ or monochlorocycloalkane~ can be prepared by reacting an alcohol with hydrogen chloride in the presence of aqueous zinc chloride. German Offensive 3332253 teaches that mixtures containing alcohols and ethers may be converted to alkyl halides by reactions with hydrogen chloride in the presence of an aluminum-zinc chloride catalyst. This reference further teache3 that small amounts of alkali metal chlorides and larger amounts of cadmium, iron and/or magnesium chlorides may be added with the zinc ~hloride to inarease the efficiency of the catalyst.
Such methods do not resolve all the existing problems. The problems relating to the manufacture of chlorinated hydrocarbons include excessive production of by-products; requirements for use of excess hydrochloric acid and excessive coking of the catalyst. An additional problem related to the use oP alumina or alum$na ~upported catalysts is the breakdown of the alumina to produce bohemite. What is needed is a non--alumina càtalyst which results in a high yield of chlorinated hydrocarbon; which permits the complete conversion of hydrochloric acid; which does not experience excessive coke formation; and which reduces the amount of by-product3 formed.
In one aspect, the preqent invention is such a hydrochlorination catalyst comprising a Group IA cat-ion, a Group IIA or IIB cation and a neutralizing number of counter anions supported on a non-alumina porous carrier. The molar ratio of the Group IA cation to the Group IIA or IIB cation is at least about 0.5:1 and no greater than about 1.5:1.
36,~67-F -2-!
2~31~
In a second aspect, the present invention is a proce~s for the hydrochlorination of hydrocarbyl com-pounds to form chlorinated hydrocarbyl compounds wherein the hydrocarbyl compounds and hydrogen chloride are contacted in the vapor phase in the presence of the catalyst described above under reaction conditions suf-ficient to form the chlorinated hydrocarbyl compounds.
The chlorinated hydrocarbyl compounds produced :~
by the practice have variou~ utilitieq as industrial chemical~ and ~olvent~. Methyl chloride, for example, - , i9 uqeful as a cataly~t carrier in low temperature polymerizations; aq a fluid for thermometric and ther-moqtatic equipment; as a methylating agent in organic qyntheqis, such as of methylcellulo~e; and as an extractant and low temperature solvent.
It i~ ~urpri~ing that the use of a catalyst supported on a non-alumina ~upport and comprising the specified molar ratio of the cations described above reqùlt~ ln a high yield of chlorinated hydrocarbyl compound~ with reduced formation of by-products and with minimal ¢oking of the cataly9t. The u~e of ths z5 specified non-alumina supported cataly~t eliminates the problem of bohemite formation while maintaining high -~
yield~.
The catalyst of the present invention is advantageously a salt of a Group IA metal (alkali : metal); a Group IIA or IIB, preferably Group IIB, metal;
and a neutralizing number of counter anions supported on : a non-alumina porou~ carrier material. Preferred Group i:
36,467-F _3_ ~:
,, .
s ~ , ,, " , , : ~ , 2G~ 4 IA metals include sodium, potassium, rubidium, lithium and cesium, with pota~sium and cesium being more pre-ferred and potaq~ium being most preferred. The preferred Group IIB metals include zinc, cadmium and mercury with zinc being more preferred. While any counter anion, -~uch as bromide, chloride and fluoride, is suitable in the catalyst of this invention, the halide~-are preferred with chloride being most pre-ferred. Other suitable anions are nitrates, ~ulfate, phosphate, acetates, oxylate and cyanides.
The molar ratio of Group IA metal to Group ~IA
or IIB metal in the salt is preferably at least about 0.5:1 and no greater than about 1.5:1. It i~ more pre-ferred that the molar ratio is at least about 0.9:1 andno greater than about 1.1:1 and most preferred that approximately equimolar portions of the two metals are used. The amount of counter anion u~ed is that which is suffl¢ient to neutralize the cations of the salt.
Any non-alumina support which will withstand the hydro¢hlorinat~on ¢onditions de~cribed herein can be used ln the pro¢e8~ of the present invention. Examples of appropriate supports include the well-known carbon supports su¢h as activated ¢arbon, carbon black, chars and ¢oke. Other suitable supports that may be used to support the catalyst include pumice, silica gel, a~bestos, diatomaceous earth, fullers earth, titania, zirconia, magnesia, magnesium silicate, silicon carbide, ~ilicalite, and silica. A preferred ~upport is silica.
A silica having a surface area between 100 m2/g and 300 m2/g and a pore volume in the range of 0.75 cc/g to 1.4 cc/g is particularly active in the process of this invention.
~jf i~
36,467-F -4_ 5 2G~)3~4 ;
The salt is suitably supported on the carrier ~-;
material by any standard impregnation technique such as that disclosed in ExperimentalMethods~nCatalyticResearch, Vol. II, edited by R. B. Anderson and P. T. Dawson, Academic Press, New York, 1978. A solution o~ both the Group IA and Group IIA or IIB metal cations and the a~qociated anions may be employed to impregnate the support material or the metal salts may be impregnated from separate solutions. The resulting cataly~t com-prising the catalytically active salt and the supportpreferably comprises from 1 to 50 weight percent of the Group IIA or IIB metal salt, e.g., ZnCl2, and from 0.5 to 30 weight percent of the Group IA metal Qalt, e.g., KCl, based on the percentage by weight of the total salts to the support. It i~ preferred to use at least about 20 and no greater than about 30 weight percent of the Group IIA or IIB metal salt and at least about 10 and no greater than about 20 weight percent of the Group IA metal salt and more preferred to use about 20 weight percent of the Group IIA or IIB metal ~alt and about 10 weight percent of the Group IA metal salt. Preferred weight percents of the two salts are selected so as to result in approximately equimolar proportions of the Group IA and Group IIA or IIB salt being used.
The proceqs of the present invention comprise~
contacting a hydrocarbon and hydrogen chloride in the presence of the aforementioned cataly~t under reaction condition~ sufficient to produce the corresponding chlo-rinated hydrocarbon. Example~ of hydrocarbons u~eful in the practice of this invention include compounds corresponding to the formula ~ , .
~ 36,467-F -5-, ,~ , - , , ., ;; . -, . .." . -. . . .~. . . . . . .
.. . .. . .
2~()314 ` -6 ROH
wherein ~ is alkyl, aryl, arylalkyl and alkylaryl. It i~ preferred that R i9 alkyl and more preferred that R
iq lower alkyl having from 1 to 5 carbon atom~. It i~
most preferred that R i_ alkyl having from 1 to 3 carbon atom3. Example~ of preferred hydrocarbyl compounds thus include methanol, ethanol and propanol with methanol being more preferred.
Molar ratio~ of hydrocarbon to hydrogen chloride useful in the practice of thi~ invention are -~
generally at least about 1:10 and no greater than about 10:1. When hydrogen chloride i~ used in exces~, it iq 15 preferred that the amount of exces~ hydrogen chloride i_ no more than about 30 molar percent. It i~ preferred that the hydro¢arbon be uqed in exceq~. When the hydrocarbon i3 used in excesq, the molar ratio of hydro¢arbon to hydrogen chloride i9 preferably no greater than about 2:1, more preferably no greater than about 1.5:1 and most preferably about 1.1:1.
The temperature range u~eful in the pra¢tice of 25 this invention ~g any at which the hydrochlorination reaction will pro¢eed. Preferably, the reactian is conducted at a temperature o~ at least about 25C and no greater than about 475C with at lea~qt 175C to no greater than 300C being more preferred. The most 30 preferred temperature range~ from at lea_t 250C to no greater than 275C. Preqqureq typically employed in the proces~ of the pre~ent invention are at lea~t about 14 p~ig (97 kPa gauge) and no greater than about 500 pqig ~(3450 kPa gauge). Preferred pressure~ are at lea~t ,' ~
; 36,467-F -6-~:
-7- :
about 35 psig (240 kPa gauge) and no greater than about 150 psig (1035 kPa gauge).
Gas hourly space velocities are suitably at least about 100 and no greater than about 10,000 hours~1, preferably at least about 300 and no greater than about 3000 hr~1.
The process may be operated in a batch mode or ¢ontinuously, although continuous operation is pre-~erred. In a preferred embodiment, vaporized methanol and hydrogen chloride are added in approximately equi-molar proportions to a fixed bed reactor containing a KZnCl3 catalyst supported on silica. The resultant products are separated by distillation.
The process of this invention is ef~ective in redu¢ing the amount of by-products ~ormed. In a pre-', ~erred embodiment wherein methanol and hydrogen chloride react to Porm methyl chloride, the production of by--products ~uch as dimethyl ether i 9 decreased. The praoess o~ the present inventlon also results in a long--llv~d catalyst. The catalyst of the present invention i~ ~table and the absence o~ alumina eliminate~ the problem of bohemite formation.
The following examples are provided to illus-trate the invention and ~hould not be interpreted as limiting it in any way. Unle~s ~tated otherwise, all parts and percentages are by weight.
' `~
:t ~ 36,467-F -7-~ :
. ,-, . ;: ; . .. . . . . .
^: . . .. . - . ~ . . . . . .
Exam~le 1 - Catalyst Preparation A silica qample waq sieved between three screenq and the fraction_ retained by 4 mesh, 5 mesh and 8 me3h, (4.75 mm, 4.00 mm, 2.36 mm, Tyler Sieve) respectively, are collected. The 8 meqh (2.36 mm, Tyler Sieve) fraction waq used in the preparation of 200 g ~amples of about 500 cubic centimeter~ each. A 200 g sample waq placed in a 2 liter di~h and dried 48 hour~
at 150C. The sample wa~ transferred to a 1 liter flutsd flacik, placed on a rotovap and cooled to 70C
under vacuum. The silica was then impregnated with a solution of 60 g of ZnCl2 and 32.81 g of KCl in a total volume of 278 cubic centimeters of water. The impregnated cataly~t wa~ returned to the 2 liter dish and air dried for 24 hour~ and then dried for an additional 25 hours at 150C.
xamDle 2 ., A three-liter portion of cataly~t, prepared a~
de~¢ribed above, waq placed into an Inconel reactor that is 20 ~eet (6 meters) long and 1.25 in¢hes (32 mm) in diameter. The reactor waCi then purged with nitrogen for 48 hours at 220C. The cataly~t wa~ then conditioned with HCl mixed with nitrogen prior to reaction with methanol. The proportion~ of methanol to hydrcgen chloride and the reaction temperature were varied a~
~hown in Table I below. The reactor effluent wa~
FOR HYDROCHLORINATION OF HYDROCARBONS
This invention relate_ to catalytio hydro- ;
chlorination processes. In particular, the invention relates to the catalytic hydrochlorination of hydro-carbyl compounds.
: Chlorinated hydrocarbons have various utilities .:- a~ lndustrial chemicals and solvents. For example, methyl chloride i8 useful aq a catalyst carrier in low temperature polymerizations; as a fluid for thermometric and thermo~tatic equipment; as a methylating agent in organlc synthesis, such as of methylcellulose; in the preparation of silicone rubberq; and as an extractant and low temperature solvent.
Method~ for the production of chlorinated ~;: hydrocarbons, such as methyl chloride, are well-known.
In a typical method for the production of methyl chlo-ride, vaporized methanol and hydrogen chloride are mixed in approximately equimolar proportions and pa~ed through a converter packed with a catalyst such as alumina gel or zinc chloride on activated carbon to form - methyl chloride. Other known methods involve reactions : 25 in the liquid phaqe uqing an aqueou~ solution of , :
~ ~
~ 36~467-F -1-h::
2~ 3~4 catalyst. For example, U.S. Patent 4,073,816 teaches that monochloroalkane~ or monochlorocycloalkane~ can be prepared by reacting an alcohol with hydrogen chloride in the presence of aqueous zinc chloride. German Offensive 3332253 teaches that mixtures containing alcohols and ethers may be converted to alkyl halides by reactions with hydrogen chloride in the presence of an aluminum-zinc chloride catalyst. This reference further teache3 that small amounts of alkali metal chlorides and larger amounts of cadmium, iron and/or magnesium chlorides may be added with the zinc ~hloride to inarease the efficiency of the catalyst.
Such methods do not resolve all the existing problems. The problems relating to the manufacture of chlorinated hydrocarbons include excessive production of by-products; requirements for use of excess hydrochloric acid and excessive coking of the catalyst. An additional problem related to the use oP alumina or alum$na ~upported catalysts is the breakdown of the alumina to produce bohemite. What is needed is a non--alumina càtalyst which results in a high yield of chlorinated hydrocarbon; which permits the complete conversion of hydrochloric acid; which does not experience excessive coke formation; and which reduces the amount of by-product3 formed.
In one aspect, the preqent invention is such a hydrochlorination catalyst comprising a Group IA cat-ion, a Group IIA or IIB cation and a neutralizing number of counter anions supported on a non-alumina porous carrier. The molar ratio of the Group IA cation to the Group IIA or IIB cation is at least about 0.5:1 and no greater than about 1.5:1.
36,~67-F -2-!
2~31~
In a second aspect, the present invention is a proce~s for the hydrochlorination of hydrocarbyl com-pounds to form chlorinated hydrocarbyl compounds wherein the hydrocarbyl compounds and hydrogen chloride are contacted in the vapor phase in the presence of the catalyst described above under reaction conditions suf-ficient to form the chlorinated hydrocarbyl compounds.
The chlorinated hydrocarbyl compounds produced :~
by the practice have variou~ utilitieq as industrial chemical~ and ~olvent~. Methyl chloride, for example, - , i9 uqeful as a cataly~t carrier in low temperature polymerizations; aq a fluid for thermometric and ther-moqtatic equipment; as a methylating agent in organic qyntheqis, such as of methylcellulo~e; and as an extractant and low temperature solvent.
It i~ ~urpri~ing that the use of a catalyst supported on a non-alumina ~upport and comprising the specified molar ratio of the cations described above reqùlt~ ln a high yield of chlorinated hydrocarbyl compound~ with reduced formation of by-products and with minimal ¢oking of the cataly9t. The u~e of ths z5 specified non-alumina supported cataly~t eliminates the problem of bohemite formation while maintaining high -~
yield~.
The catalyst of the present invention is advantageously a salt of a Group IA metal (alkali : metal); a Group IIA or IIB, preferably Group IIB, metal;
and a neutralizing number of counter anions supported on : a non-alumina porou~ carrier material. Preferred Group i:
36,467-F _3_ ~:
,, .
s ~ , ,, " , , : ~ , 2G~ 4 IA metals include sodium, potassium, rubidium, lithium and cesium, with pota~sium and cesium being more pre-ferred and potaq~ium being most preferred. The preferred Group IIB metals include zinc, cadmium and mercury with zinc being more preferred. While any counter anion, -~uch as bromide, chloride and fluoride, is suitable in the catalyst of this invention, the halide~-are preferred with chloride being most pre-ferred. Other suitable anions are nitrates, ~ulfate, phosphate, acetates, oxylate and cyanides.
The molar ratio of Group IA metal to Group ~IA
or IIB metal in the salt is preferably at least about 0.5:1 and no greater than about 1.5:1. It i~ more pre-ferred that the molar ratio is at least about 0.9:1 andno greater than about 1.1:1 and most preferred that approximately equimolar portions of the two metals are used. The amount of counter anion u~ed is that which is suffl¢ient to neutralize the cations of the salt.
Any non-alumina support which will withstand the hydro¢hlorinat~on ¢onditions de~cribed herein can be used ln the pro¢e8~ of the present invention. Examples of appropriate supports include the well-known carbon supports su¢h as activated ¢arbon, carbon black, chars and ¢oke. Other suitable supports that may be used to support the catalyst include pumice, silica gel, a~bestos, diatomaceous earth, fullers earth, titania, zirconia, magnesia, magnesium silicate, silicon carbide, ~ilicalite, and silica. A preferred ~upport is silica.
A silica having a surface area between 100 m2/g and 300 m2/g and a pore volume in the range of 0.75 cc/g to 1.4 cc/g is particularly active in the process of this invention.
~jf i~
36,467-F -4_ 5 2G~)3~4 ;
The salt is suitably supported on the carrier ~-;
material by any standard impregnation technique such as that disclosed in ExperimentalMethods~nCatalyticResearch, Vol. II, edited by R. B. Anderson and P. T. Dawson, Academic Press, New York, 1978. A solution o~ both the Group IA and Group IIA or IIB metal cations and the a~qociated anions may be employed to impregnate the support material or the metal salts may be impregnated from separate solutions. The resulting cataly~t com-prising the catalytically active salt and the supportpreferably comprises from 1 to 50 weight percent of the Group IIA or IIB metal salt, e.g., ZnCl2, and from 0.5 to 30 weight percent of the Group IA metal Qalt, e.g., KCl, based on the percentage by weight of the total salts to the support. It i~ preferred to use at least about 20 and no greater than about 30 weight percent of the Group IIA or IIB metal salt and at least about 10 and no greater than about 20 weight percent of the Group IA metal salt and more preferred to use about 20 weight percent of the Group IIA or IIB metal ~alt and about 10 weight percent of the Group IA metal salt. Preferred weight percents of the two salts are selected so as to result in approximately equimolar proportions of the Group IA and Group IIA or IIB salt being used.
The proceqs of the present invention comprise~
contacting a hydrocarbon and hydrogen chloride in the presence of the aforementioned cataly~t under reaction condition~ sufficient to produce the corresponding chlo-rinated hydrocarbon. Example~ of hydrocarbons u~eful in the practice of this invention include compounds corresponding to the formula ~ , .
~ 36,467-F -5-, ,~ , - , , ., ;; . -, . .." . -. . . .~. . . . . . .
.. . .. . .
2~()314 ` -6 ROH
wherein ~ is alkyl, aryl, arylalkyl and alkylaryl. It i~ preferred that R i9 alkyl and more preferred that R
iq lower alkyl having from 1 to 5 carbon atom~. It i~
most preferred that R i_ alkyl having from 1 to 3 carbon atom3. Example~ of preferred hydrocarbyl compounds thus include methanol, ethanol and propanol with methanol being more preferred.
Molar ratio~ of hydrocarbon to hydrogen chloride useful in the practice of thi~ invention are -~
generally at least about 1:10 and no greater than about 10:1. When hydrogen chloride i~ used in exces~, it iq 15 preferred that the amount of exces~ hydrogen chloride i_ no more than about 30 molar percent. It i~ preferred that the hydro¢arbon be uqed in exceq~. When the hydrocarbon i3 used in excesq, the molar ratio of hydro¢arbon to hydrogen chloride i9 preferably no greater than about 2:1, more preferably no greater than about 1.5:1 and most preferably about 1.1:1.
The temperature range u~eful in the pra¢tice of 25 this invention ~g any at which the hydrochlorination reaction will pro¢eed. Preferably, the reactian is conducted at a temperature o~ at least about 25C and no greater than about 475C with at lea~qt 175C to no greater than 300C being more preferred. The most 30 preferred temperature range~ from at lea_t 250C to no greater than 275C. Preqqureq typically employed in the proces~ of the pre~ent invention are at lea~t about 14 p~ig (97 kPa gauge) and no greater than about 500 pqig ~(3450 kPa gauge). Preferred pressure~ are at lea~t ,' ~
; 36,467-F -6-~:
-7- :
about 35 psig (240 kPa gauge) and no greater than about 150 psig (1035 kPa gauge).
Gas hourly space velocities are suitably at least about 100 and no greater than about 10,000 hours~1, preferably at least about 300 and no greater than about 3000 hr~1.
The process may be operated in a batch mode or ¢ontinuously, although continuous operation is pre-~erred. In a preferred embodiment, vaporized methanol and hydrogen chloride are added in approximately equi-molar proportions to a fixed bed reactor containing a KZnCl3 catalyst supported on silica. The resultant products are separated by distillation.
The process of this invention is ef~ective in redu¢ing the amount of by-products ~ormed. In a pre-', ~erred embodiment wherein methanol and hydrogen chloride react to Porm methyl chloride, the production of by--products ~uch as dimethyl ether i 9 decreased. The praoess o~ the present inventlon also results in a long--llv~d catalyst. The catalyst of the present invention i~ ~table and the absence o~ alumina eliminate~ the problem of bohemite formation.
The following examples are provided to illus-trate the invention and ~hould not be interpreted as limiting it in any way. Unle~s ~tated otherwise, all parts and percentages are by weight.
' `~
:t ~ 36,467-F -7-~ :
. ,-, . ;: ; . .. . . . . .
^: . . .. . - . ~ . . . . . .
Exam~le 1 - Catalyst Preparation A silica qample waq sieved between three screenq and the fraction_ retained by 4 mesh, 5 mesh and 8 me3h, (4.75 mm, 4.00 mm, 2.36 mm, Tyler Sieve) respectively, are collected. The 8 meqh (2.36 mm, Tyler Sieve) fraction waq used in the preparation of 200 g ~amples of about 500 cubic centimeter~ each. A 200 g sample waq placed in a 2 liter di~h and dried 48 hour~
at 150C. The sample wa~ transferred to a 1 liter flutsd flacik, placed on a rotovap and cooled to 70C
under vacuum. The silica was then impregnated with a solution of 60 g of ZnCl2 and 32.81 g of KCl in a total volume of 278 cubic centimeters of water. The impregnated cataly~t wa~ returned to the 2 liter dish and air dried for 24 hour~ and then dried for an additional 25 hours at 150C.
xamDle 2 ., A three-liter portion of cataly~t, prepared a~
de~¢ribed above, waq placed into an Inconel reactor that is 20 ~eet (6 meters) long and 1.25 in¢hes (32 mm) in diameter. The reactor waCi then purged with nitrogen for 48 hours at 220C. The cataly~t wa~ then conditioned with HCl mixed with nitrogen prior to reaction with methanol. The proportion~ of methanol to hydrcgen chloride and the reaction temperature were varied a~
~hown in Table I below. The reactor effluent wa~
3 an~lyzed by ga~ chromatography to determine the con- i ver~ion obtained and the amount of dimethyl ether pro-duced relative to the amount of methyl chloride pro-duced. The reqult~ obtained are ~hown in Table I below.
~-.
; 36,467-F -8-:
g 2&~314 TABLE I
Run i~g~h~l ~Cl, in Temp version~ D~ t~C~
1 8.00 (3.6)10.00 (4.5) 220 96.6 11726 2 8.00 (3.6) 10.00 (4.5) 2~5 96.4 11545 3 3.92 (1.8) 5.5~ ~2.5) 220 99.0 6981 0 4 3.92 (1.8) 4.91 (2.2) 220 98.2 8957 S 7.46 (3.4) 10.57 (4.8) 220 98.4 7713 6 5.83 (2.6) 7.78 (3.5) 220 98.4 8161 7 8.00 (3.6) 10.00 (4.5) 220 93.1 13780 8 4.14 (1.9) 4.95 (2.2) 220 94.3 13441 9 8.00 (3.6) 10.00 (4.5) 220 93.4 14065
~-.
; 36,467-F -8-:
g 2&~314 TABLE I
Run i~g~h~l ~Cl, in Temp version~ D~ t~C~
1 8.00 (3.6)10.00 (4.5) 220 96.6 11726 2 8.00 (3.6) 10.00 (4.5) 2~5 96.4 11545 3 3.92 (1.8) 5.5~ ~2.5) 220 99.0 6981 0 4 3.92 (1.8) 4.91 (2.2) 220 98.2 8957 S 7.46 (3.4) 10.57 (4.8) 220 98.4 7713 6 5.83 (2.6) 7.78 (3.5) 220 98.4 8161 7 8.00 (3.6) 10.00 (4.5) 220 93.1 13780 8 4.14 (1.9) 4.95 (2.2) 220 94.3 13441 9 8.00 (3.6) 10.00 (4.5) 220 93.4 14065
4.24 (1.9) 4.84 (2.2) 220 91.3 16209 11 9.81 (4.4) 10.34 (4.7) 220 93.6 13900 ~ Conversion Oe methanol to methyl chloride ~art# o~ dimethyl ether producod per million parts of methyl ~hloride :
The data abovs illu~Qtrate that the uQe of the catalytic proceQs o~ this invention re~ultq in a high rate of conversion of methanol. RunQ 1 and 2 demon-strate that an increaQe in the reaction temperature from 220C to 235C has little effe¢t on conver_ion or dimethyl ether production. Run_ 3 and 4 demonqtrats ths effect of varying the ratio of msthanol to hydrogen chloride. Run 3 representQ a 25 percent molar exceqq of hydrogen chloride whils Run 4 shows a 10 psrcent molar exce~s. At the 10 percent exce_s level, the conversion decrea-qes and the dimethyl ether production increaseQ
36~467-F -9_ .. . . . .
Z~iO31~
--1 o although in either case the conversion is high and the dimethyl ether production iq low. Runs 8, 10 and 11 show the effect of decreasing the molar proportion of HCl until methanol is used in excess. The ratios of methanol to HCl change from 1:1.05 in Run 8 to 1:1 in ~un 10 and to 1.13:1 and follow the trend shown in Run~
3 and 4. These trends indicate that high conversion and acceptably low dimethyl ether production may be obtained when methanol is used in excess. Run~ 1, 7 and 9 are all identical and demonstrate that after a breaking in period, the catalyst is stable within the time frame of the experiment.
:
- .
36,467-F -10-~' ' . . .
~, ~ .' . ' , . ' , .
The data abovs illu~Qtrate that the uQe of the catalytic proceQs o~ this invention re~ultq in a high rate of conversion of methanol. RunQ 1 and 2 demon-strate that an increaQe in the reaction temperature from 220C to 235C has little effe¢t on conver_ion or dimethyl ether production. Run_ 3 and 4 demonqtrats ths effect of varying the ratio of msthanol to hydrogen chloride. Run 3 representQ a 25 percent molar exceqq of hydrogen chloride whils Run 4 shows a 10 psrcent molar exce~s. At the 10 percent exce_s level, the conversion decrea-qes and the dimethyl ether production increaseQ
36~467-F -9_ .. . . . .
Z~iO31~
--1 o although in either case the conversion is high and the dimethyl ether production iq low. Runs 8, 10 and 11 show the effect of decreasing the molar proportion of HCl until methanol is used in excess. The ratios of methanol to HCl change from 1:1.05 in Run 8 to 1:1 in ~un 10 and to 1.13:1 and follow the trend shown in Run~
3 and 4. These trends indicate that high conversion and acceptably low dimethyl ether production may be obtained when methanol is used in excess. Run~ 1, 7 and 9 are all identical and demonstrate that after a breaking in period, the catalyst is stable within the time frame of the experiment.
:
- .
36,467-F -10-~' ' . . .
~, ~ .' . ' , . ' , .
Claims (28)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A hydrochlorination catalyst comprising a Group IA cation and a Group IIA or Group IIB cation in a molar ratio of at least about 0.5:1 and no greater than about 1.5:1 and a neutralizing number of counter anions supported on a non-alumina porous carrier.
2. The catalyst of Claim 1 wherein the Group IA cation is a cation of a metal selected from potassium and cesium.
3. The catalyst of Claim 2 wherein the Group IA cation is a potassium cation.
4. The catalyst of Claim 1 wherein the Group IIB cation is a zinc cation.
5. The catalyst of Claim 1 wherein the porous carrier is silica.
6. The catalyst of Claim 5 wherein the silica has a surface area of between 100 m2/g and 300 m2/g and a pore volume in the range of 0.75 cc/g to 1.4 cc/g.
7. The catalyst of Claim 1 wherein the counter ion is chloride.
8. The catalyst of Claim 1 wherein the ratio of Group IA cation to Group IIA or Group IIB cation is at least about 0.9:1 and no greater than about 1.1:1.
9. The catalyst of Claim 8 wherein the ratio of Group IA cation to Group IIA or Group IIB cation is about 1:1.
10. The catalyst of Claim 8 wherein the Group IA cation is potassium, the Group IIB cation is zinc, the counter ion is chloride and the porous carrier is silica.
11. A process for the hydrochlorination of alkanols corresponding to the formula ROH
wherein R is alkyl, aryl, arylalkyl or alkylaryl, to form chlorinated compounds comprising contacting the alkanol and hydrogen chloride at a molar ratio of at least about 1:10 and no greater than about 10:1 in the vapor phase in the presence of a hydrochlorination catalyst, said catalyst comprising a first cation selected from potassium, cesium, sodium, rubidium and lithium and a second cation selected Prom zinc, cadmium and mercury in a molar ratio of first cation to second cation of at least about 0.5:1 and no greater than about 1.5:1 and a neutralizing number of counter anions supported on a non-alumina porous carrier under reaction conditions sufficient to form the chlorinated compounds corresponding to the starting alkanols.
wherein R is alkyl, aryl, arylalkyl or alkylaryl, to form chlorinated compounds comprising contacting the alkanol and hydrogen chloride at a molar ratio of at least about 1:10 and no greater than about 10:1 in the vapor phase in the presence of a hydrochlorination catalyst, said catalyst comprising a first cation selected from potassium, cesium, sodium, rubidium and lithium and a second cation selected Prom zinc, cadmium and mercury in a molar ratio of first cation to second cation of at least about 0.5:1 and no greater than about 1.5:1 and a neutralizing number of counter anions supported on a non-alumina porous carrier under reaction conditions sufficient to form the chlorinated compounds corresponding to the starting alkanols.
12. The process of Claim 11 wherein the alkanol is a lower alkanol.
13. The process of Claim 12 wherein the lower alkanol is methanol.
14. The process of Claim 13 wherein the molar ratio of methanol to hydrogen chloride is at least about 1.1:1 and no greater than about 2:1.
15. The process of Claim 14 wherein the molar ratio of methanol to hydrogen chloride is at least about 1.1:1 and no greater than about 1.5:1.
16. The process Or Claim 11 wherein the reaction temperature is at least about 175°C and no greater than about 300°C.
17. The process of Claim 16 wherein the reac-tion temperature is at least about 250°C and no greater than about 275°C.
18. The process of Claim 11 wherein the reaction pressure is at least about 35 psig (240 kPa gauge) and no greater than about 150 psig (1035 kPa gauge).
19. The process Or Claim 11 wherein the first cation of the catalyst is a cation of a metal selected from potassium and cesium.
20. The process of Claim 19 wherein the second cation of the catalyst is a zinc cation.
21. The process of Claim 20 wherein the counter ion of the catalyst is chloride.
22. The process of Claim 21 wherein the ratio of potassium to zinc is at least about 0.9:1 and no greater than about 1.1:1.
23. The process of Claim 22 wherein the ratio of potassium to zinc is about 1:1.
24. The process of Claim 23 wherein the catalyst is KCl and ZNCl2 supported on silica having surface area between 100 m2/g and 300 m2/g and a pore volume in the range of 0.75 cc/g to 1.4 cc/g.
25. The process of Claim 24 wherein methanol and hydrogen chloride are contacted in the vapor phase at a temperature of about 250°C in the presence of a catalyst comprising KCl and ZNCl2 supported on silica under reaction conditions sufficient to produce methyl chloride.
26. The process of Claim 19 wherein the first cation of the catalyst is potassium.
27. The process of Claim 13 wherein the molar ratio of methanol to hydrogen chloride ranges from about 2:1 to about 1:1.3.
28. The process of Claim 27 wherein the molar ratio of methanol to hydrogen chloride ranges from about 1.1:1 to about 1:1.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002010314A CA2010314A1 (en) | 1988-08-24 | 1990-02-19 | Process and catalyst for hydrochlorination of hydrocarbons |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/235,579 US4935565A (en) | 1988-08-24 | 1988-08-24 | Process and catalyst for hydrochlorination of hydrocarbons |
| CA002010314A CA2010314A1 (en) | 1988-08-24 | 1990-02-19 | Process and catalyst for hydrochlorination of hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2010314A1 true CA2010314A1 (en) | 1991-08-19 |
Family
ID=25673960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002010314A Abandoned CA2010314A1 (en) | 1988-08-24 | 1990-02-19 | Process and catalyst for hydrochlorination of hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2010314A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112718007A (en) * | 2021-02-19 | 2021-04-30 | 李俊乐 | Catalyst for producing nonenylated diphenylamine antioxidant and preparation method thereof |
-
1990
- 1990-02-19 CA CA002010314A patent/CA2010314A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112718007A (en) * | 2021-02-19 | 2021-04-30 | 李俊乐 | Catalyst for producing nonenylated diphenylamine antioxidant and preparation method thereof |
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