Gas phase process for chlorotrifluoroethylene
阅读说明：本技术 三氟氯乙烯的气相方法 (Gas phase process for chlorotrifluoroethylene ) 是由 哈里达桑·K·奈尔 拉吉夫·拉特纳·辛格 格伦·马蒂斯 于 2019-02-05 设计创作，主要内容包括：本发明涉及一种在存在催化剂的情况下并且任选地在存在烯烃或烷烃的情况下通过对卤代乙烷进行气相脱氯来制备卤代乙烯、并且优选全卤代乙烯的方法。在具体方面,本发明涉及一种用于制备三氟氯乙烯(CTFE)的气相方法。更具体地,本发明涉及一种在存在烯烃或烷烃和催化剂的情况下通过脱氯从1,1,2-三氯-1,2,2-三氟乙烷(CFC-113)制备CTFE的气相方法。(The present invention relates to a process for the preparation of vinyl halides, and preferably perhalogenated vinyl, by gas-phase dechlorination of a halogenated ethane in the presence of a catalyst and optionally in the presence of an alkene or alkane. In a particular aspect, the present invention relates to a gas phase process for the preparation of Chlorotrifluoroethylene (CTFE). More particularly, the present invention relates to a gas phase process for the preparation of CTFE by dechlorination from 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CFC-113) in the presence of an alkene or alkane and a catalyst.)
1. A process for the production of halogenated ethylene, which process comprises the vapour phase dechlorination of a halogenated ethane in the presence of a catalyst and optionally an alkane or alkene, wherein the halogenated ethane or perhalogenated ethane comprises at least two chlorine atoms on adjacent carbon atoms, and wherein the catalyst is selected from: (a) transition metal oxides such as iron (III) oxide, nickel (II) oxide, copper (II) oxide and mixtures thereof, and (b) transition metal fluorides and chlorides such as copper (II) chloride or fluoride and iron chloride or fluoride.
2. A process for producing a vinyl halide having the formula:
CFmCln＝CFxCly
wherein
m is 0 to 2, n is 0 to 2, and m + n is 2; and is
x is 0 to 2, y is 0 to 2, and x + y is 2;
the process comprises the vapor phase dechlorination of a halogenated ethane having the formula:
CFmCln＝CFxCly
wherein
m is 0 to 2, n is 0 to 2, and m + n is 2; and is
x is 0 to 2, y is 0 to 2, and x + y is 2;
the catalyst is selected from: (a) transition metal oxides such as iron (III) oxide, nickel (II) oxide, copper (II) oxide and mixtures thereof, and (b) transition metal fluorides and chlorides such as copper (II) chloride and copper (II) fluoride.
3. The method of claim 1 or 2, wherein the catalyst comprises Fe2O3、NiO、CuO、CuF2、CuCl2And mixtures thereof.
4. The process according to any one of claims 1 to 3, wherein the catalyst is selected from Fe on carbon2O3/NiO, carbon-supported Fe2O3CuO, carbon-supported CuF2And carbon-supported CuCl2。
5. The process of any one of claims 1 to 4, wherein the dechlorination reaction comprises an alkane having from 1 to 6 carbon atoms.
6. The process of any one of claims 1 to 4, wherein the dechlorination reaction comprises an olefin having from 1 to 3 carbon atoms.
7. The process of any one of claims 1 to 6, wherein the dechlorination reaction temperature is from about 300 ℃ to about 650 ℃.
8. The process of any one of claims 1 to 6, wherein the dechlorination reaction temperature is from about 400 ℃ to about 600 ℃.
9. The process of any one of claims 1 to 8, wherein the dechlorination reaction is further in the presence of nitrogen (N)2) In the case of a gas.
10. The process of any one of claims 1 to 9, wherein the dechlorination reaction provides a haloalkane product with a selectivity of greater than about 75%.
11. A process for the production of Chlorotrifluoroethylene (CTFE), the process comprising the gas phase dechlorination of 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CFC-113) in the presence of a catalyst and optionally an alkane or alkene, wherein the catalyst is selected from the group consisting of: (a) transition metal oxides such as iron (III) oxide, nickel (II) oxide, copper (II) oxide and mixtures thereof, and (b) transition metal fluorides and chlorides such as copper (II) chloride and copper (II) fluoride.
12. The method of claim 11, wherein the catalyst comprises Fe2O3、NiO、CuO、CuF2、CuCl2And mixtures thereof.
13. The process of any one of claims 11 to 12, wherein the dechlorination reaction comprises an olefin having 2 to 6 carbon atoms.
14. The process of any one of claims 11 to 13, wherein the dechlorination reaction is at a temperature of between about 400 ℃ and about 650 ℃.
15. The process of any one of claims 11 to 14, wherein the dechlorination reaction provides a CTFE product with a selectivity of greater than about 75%.
Technical Field
The invention relates to a method for producing halogenated ethylene, and preferably perhalogenated ethylene, by dechlorinating halogenated ethane, comprising reacting halogenated ethane in the gas phase in the presence of a catalyst. In a particular aspect, the present invention relates to a gas phase process for the preparation of chlorotrifluoroethylene ("CTFE"). More particularly, the present invention relates to a gas phase process for the preparation of CTFE by dechlorination from 1,1, 2-trichloro-1, 2, 2-trifluoroethane ("CFC-113") in the presence of a catalyst.
Background
CTFE is an important commercial monomer in fluoropolymer production.
Various methods have been used to prepare CTFE. These processes have certain disadvantages, including the consumption of expensive materials, low product yields, or both. For example, CTFE has been prepared by a liquid phase process comprising dechlorination of 1,1, 2-trichloro-1, 2, 2-trifluoroethane using zinc. Although CTFE can be obtained in good yield by this method, it is cumbersome and expensive to handle the zinc chloride by-product. CTFE is also prepared by co-pyrolysis of dichlorofluoromethane and chlorodifluoromethane. However, co-pyrolysis provides low CTFE yields.
CTFE has been prepared by the vapor phase dechlorination of 1,1, 2-trichloro-1, 2, 2-trifluoroethane with hydrogen in the presence of various activated carbon catalysts. In a gas phase process using activated carbon, the space velocity cannot be greater than about 500hr-1Otherwise, low productivity results. Already hasIt is proposed to perform gas phase dechlorination using a Pd catalyst, but Pd is expensive and may be deactivated in a short reaction time, and the reaction is performed in a contact time of 10 to 60 seconds, and thus productivity is low. Furthermore, the CTFE yields of these catalysts are unsatisfactory.
The use of a gas phase dechlorination process to produce CTFE is disclosed in US 4,155,941. The main disadvantages of this process are the reduced conversion of the starting material, the low yield of CTFE product and/or the large formation of undesired materials (CF)2＝CCl2) (in the presence of Al2O3/FeCl3In some cases of the catalyst, the catalyst may,>70％)。
accordingly, applicants have recognized a continuing need in the art for further improved methods for producing CTFE. The present invention provides a process for producing vinyl halides, and preferably perhaloethylenes, and most preferably CTFE, with good selectivity and conversion while maintaining cost effectiveness from a materials and equipment perspective.
Disclosure of Invention
The present invention provides a process for the production of vinyl halides, and preferably perhalogenated ethylene, which comprises dechlorinating one or more vinyl halides in the vapour phase in the presence of a catalyst and at least one compound which will react in the presence of the catalyst with chlorine from the dechlorination reaction in a gaseous reaction mixture, the at least one compound preferably being an alkene or an alkane.
The present invention also provides a gas phase process for the production of CTFE comprising contacting 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF) in the gas phase in the presence of a catalyst2Cl-CFCl2(ii) a CFC-113) and at least one alkane (such as methane, ethane, propane, isobutene, etc.) or alkene (such as ethylene, propylene, butene, etc.). For convenience, the method according to this paragraph is sometimes referred to herein as method 1.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a composition comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF)2Cl-CFCl2(ii) a CFC-113) and at least one alkane (such asMethane, ethane, propane, isobutylene, etc.); and (b) reacting the reaction mixture in the presence of a catalyst. For convenience, the method according to this paragraph is sometimes referred to herein as method 2.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a composition comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF)2Cl-CFCl2(ii) a CFC-113) and at least one alkane (such as methane, ethane, propane, isobutylene, etc.) or alkene (such as ethylene, propylene, butylene, etc.); and (b) reacting the reaction mixture in the presence of a catalyst at a temperature of about 300 ℃ to about 600 ℃. For convenience, the method according to this paragraph is sometimes referred to herein as method 3.
As used herein in connection with the reaction temperature, the term "about" refers to the indicated temperature +/-10 ℃.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and at least one alkane (such as methane, ethane, propane, isobutylene, etc.) or alkene (such as ethylene, propylene, butylene, etc.); (b) providing a reactor containing a catalyst; and (c) reacting the reaction mixture in the reactor in the presence of the catalyst at a temperature of about 400 ℃ to about 600 ℃. For convenience, the method according to this paragraph is sometimes referred to herein as method 4.
The present invention also provides a gas phase process for the production of CTFE comprising reacting 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and an alkane having 1 to 3 carbon atoms in the gas phase in the presence of a catalyst. For convenience, the method according to this paragraph is sometimes referred to herein as method 5. For convenience, alkanes having 1 to 3 carbon atoms are referred to herein as "C1-C3" alkanes for convenience.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and an alkane having 1 to 3 carbon atoms; and (b) reacting the reaction mixture in the presence of a catalyst. For convenience, the method according to this paragraph is sometimes referred to herein as method 6.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and a C1-C3 alkane; and (b) reacting the reaction mixture in the presence of a catalyst at a temperature of about 400 ℃ to about 600 ℃. For convenience, the method according to this paragraph is sometimes referred to herein as method 7.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and C1-C3 alkanes, wherein the reaction mixture comprises less than 1 weight percent alkanes and is substantially free of 1,1, 1-trichloro-2, 2, 2-trifluoroethane (CFC-113 a); and (b) reacting the reaction mixture in the presence of a catalyst at a temperature of about 400 ℃ to about 600 ℃. For convenience, the method according to this paragraph is sometimes referred to herein as method 8.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and an alkane having 1 to 6 carbon atoms; and (b) reacting the reaction mixture in the presence of a catalyst to produce a reaction product comprising at least about 74% CTFE and substantially free of 2-chloro-1, 1-difluoroethylene (HCFC-1122). For convenience, the method according to this paragraph is sometimes referred to herein as method 9.
The present invention also provides a gas phase process for the production of CTFE comprising reacting 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and an alkane having 1 to 6 carbon atoms in the gas phase in the presence of a catalyst. For convenience, the method according to this paragraph is sometimes referred to herein as method 10. For convenience, alkanes having 1 to 6 carbon atoms are referred to herein as "C1-C6" alkanes for convenience.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and an alkane having 1 to 6 carbon atoms; and (b) reacting the reaction mixture in the presence of a catalyst. For convenience, the method according to this paragraph is sometimes referred to herein as method 11.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and a C1-C6 alkane; and (b) reacting the reaction mixture in the presence of a catalyst at a temperature of about 400 ℃ to about 600 ℃. For convenience, the method according to this paragraph is sometimes referred to herein as method 12.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and an alkane having 1 to 6 carbon atoms; and (b) reacting the reaction mixture in the presence of a catalyst to produce a reaction product comprising at least about 74% CTFE and substantially free of 2-chloro-1, 1-difluoroethylene (HCFC-1122). For convenience, the method according to this paragraph is sometimes referred to herein as method 13.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and an alkane having 1 to 3 carbon atoms; and (b) reacting the reaction mixture in the presence of a catalyst at a temperature of about 400 ℃ to about 600 ℃ to produce a reaction product comprising at least about 74% CTFE and substantially free of 2-chloro-1, 1-difluoroethylene (HCFC-1122). For convenience, the method according to this paragraph is sometimes referred to herein as method 14.
The present invention also provides a gas phase process for producing CTFE, the process comprising: (a) providing a reaction mixture comprising 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CF2Cl-CFCl 2; CFC-113) and an alkane having 1 to 6 carbon atoms; and (b) reacting the reaction mixture in the presence of a catalyst at a temperature of about 400 ℃ to about 600 ℃ to produce a reaction product comprising at least about 74% CTFE and substantially free of 2-chloro-1, 1-difluoroethylene (HCFC-1122). For convenience, the method according to this paragraph is sometimes referred to herein as method 15.
The process of the present invention (including each of the processes 1 to 15) preferably uses a catalyst comprising one or more of a transition metal oxide, a transition metal chloride and a transition metal fluoride. For convenience, the catalyst according to this paragraph is sometimes referred to herein as catalyst 1.
The process of the present invention (including each of the processes 1 to 15) preferably uses a catalyst comprising Fe2O3And/or NiO. For convenience, the catalyst according to this paragraph is sometimes referred to herein as catalyst 2.
The process of the present invention (including each of the processes 1 to 15) preferably uses a catalyst comprising Fe supported on carbon or activated carbon2O3And/or NiO. For convenience, the catalyst according to this paragraph is sometimes referred to herein as catalyst 3.
The process of the present invention (including each of the processes 1 to 15) preferably uses a catalyst comprising a transition metal fluoride. For convenience, the catalyst according to this paragraph is sometimes referred to herein as catalyst 4.
The process of the present invention (including each of the processes 1 to 15) preferably uses a catalyst comprising a transition metal chloride. For convenience, the catalyst according to this paragraph is sometimes referred to herein as catalyst 5.
The process of the present invention (including each of processes 1 through 15, and including each of processes 1 through 15 utilizing each of catalysts 1 through 5) achieves a perhaloalkane conversion of at least about 30%.
The process of the present invention (including each of processes 1 through 15, and including each of processes 1 through 15 utilizing each of catalysts 1 through 5) achieves a perhaloalkane conversion of at least about 40%.
The process of the present invention (including each of processes 1 through 15, and including each of processes 1 through 15 utilizing each of catalysts 1 through 5) achieves a perhaloalkane conversion of at least about 50%.
The process of the present invention (including each of processes 1 through 15, and including each of processes 1 through 15 utilizing each of catalysts 1 through 5) achieves a perhaloalkane conversion of at least about 60%.
The process of the present invention (including each of processes 1 through 15, and including each of processes 1 through 15 utilizing each of catalysts 1 through 5) achieves a perhaloalkane conversion of at least about 70%.
The process of the present invention (including each of processes 1 through 15, and including each of processes 1 through 15 utilizing each of catalysts 1 through 5) achieves a perhaloalkane conversion of at least about 80%.
The process of the present invention (including each of the processes 1 to 15, and including each of the processes 1 to 15 using each of the catalysts 1 to 5) is carried out continuously in a preferred embodiment.
Detailed Description
The present invention provides a process for the production of ethylene halides, and in particular perhalogenated ethylene, by dechlorination of an ethylene halide, which process comprises reacting the ethylene halide with one or more alkenes, alkanes in the vapour phase in the presence of a catalyst. The gas phase process preferably comprises ortho-dechlorination of a halogenated ethane in the presence of a catalyst to provide a halogenated ethylene.
In one aspect of the invention, alkanes and/or alkenes are used in gas phase reactions to react with chlorine produced by dechlorination.
The haloethane starting material has two or more chlorine atoms on adjacent carbon atoms that are eliminated during the gas phase dechlorination process. In a preferred aspect of the process, the haloethane starting material is a perhaloethane having at least two chlorine atoms on adjacent carbons with the remainder of the halogens being fluorine atoms. In a preferred aspect of the process, the halogenated ethane is a perhalogenated ethane corresponding to the formula:
CFaClb-CFdClf
wherein
a is 0 to 3, b is 1 to 3, and a + b is 3;
d is 0 to 3, f is 1 to 3, and d + f is 3; and is
b + f is 2 to 6.
Preferred perhaloethanes include 1, 2-dichlorotetrafluoroethane (fluorocarbon 114) and 1,1, 2-trichloro-1, 2, 2-trifluoroethane (fluorocarbon 113), with 1,1, 2-trichloro-1, 2, 2-trifluoroethane being particularly preferred. When two chlorines are removed from these preferred halogenated hydrocarbons, the product is a perhalogenated ethylene, including for example tetrafluoroethylene or CTFE.
The gas phase process produces vinyl halides, and preferably perhaloethylenes. In a preferred aspect of the process, the product is a perhalogenated ethylene corresponding to the formula:
CFmCln＝CFxCly
wherein
m is 0 to 2, n is 0 to 2, and m + n is 2; and is
x is 0 to 2, y is 0 to 2, and x + y is 2.
In addition to the haloethane starting material, the reaction mixture preferably includes chlorine (Cl) formed by dechlorination under reaction conditions2) A compound of reaction. For convenience, such compounds are sometimes referred to herein as chlorine scavengers. In preferred embodiments, the chlorine scavenger comprises one or more of an alkane or alkene.
In certain embodiments, it is preferred that the chlorine scavenger comprise methane, as the use of methane produces excellent selectivity results. When used, the alkane preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. When used, preferred alkanes include methane, ethane, propane, butane, isobutane, pentane, hexane, and the like, and particularly methane, ethane, propane, and isobutylene, most particularly methane. When used, the alkane may be a cycloalkane such as cyclopentane and cyclohexane.
When used, the olefin has 2 to 6 carbon atoms, and more preferably 2 or 3 carbon atoms. Olefins useful as chlorine scavengers in dechlorination reactions include ethylene, propylene, butylene, pentene, and the like. Alternatively, the olefin may be a cyclic olefin, such as cyclopentene and cyclohexene.
The processes of the present invention, including each of processes 1 through 15, include those wherein the molar ratio of haloethane starting material (e.g., CFC-113) to chlorine scavenger is preferably between about 1:1 to about 1:10, with between about 1:1 to about 1:3 being more preferred.
The processes of the present invention, including each of processes 1 to 15, include those wherein the molar ratio of haloethane starting material (e.g., CFC-113) to chlorine scavenger (comprising one or more of an alkane or alkene, preferably a C1-C6 alkane, and/or more preferably a C1-C3 alkane) is preferably between about 1:1 to about 1:10, with between about 1:1 to about 1:3 being more preferred.
In a preferred embodiment, the catalyst material comprises transition metal oxides, chlorides and fluorides. The transition metal used is preferably selected from one or more of group 8, group 9 or group 10 transition metal cations. The transition metal of the catalyst is preferably selected from the group consisting of Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu and Ag.
The catalyst material includes transition metal oxides such as iron (III) oxide, nickel (II) oxide, copper (II) oxide, and mixtures thereof. They also include transition metal fluorides and chlorides such as copper (II) chloride, copper (II) fluoride, iron (III) chloride and iron (III) fluoride.
More preferred are iron compounds having a valence of 3 (including iron (III) oxide), nickel (II) compounds (including NiO), and mixtures thereof, and copper (II) compounds (including CuO, CuF)2And CuCl2)。
The catalyst may be used on a support. Preferred supports include carbon, which may be of the commercially available granular or particulate type. The catalyst loading on the support may be from about 2% to about 25% or from about 5% to about 20% on the support.
Particularly preferred combinations of catalyst and support include iron (III) oxide on carbon/nickel (II) oxide, iron (III) oxide on carbon/copper (II) oxide, copper (II) fluoride on carbon, and copper (II) chloride on carbon.
The catalyst may optionally be regenerated in situ. Regeneration of the catalyst may be accomplished by passing an oxidant over the catalyst (e.g., by passing air or oxygen (optionally diluted with nitrogen) over the catalyst). Depending on the size of the reactor, regeneration may be carried out at a temperature of from about 400 ℃ to about 650 ℃, preferably from about 500 ℃ to about 625 ℃, for from about 4 hours to about 48 hours.
The reaction may be carried out in any reactor suitable for gas phase dechlorination reactions. Preferably, the reactor is constructed of materials resistant to the corrosive effects of chlorine, catalysts or byproducts, such as stainless steel, hastelloy, inconel, monel, and fluoropolymer lined vessels.
The processes of the present invention, including each of processes 1 to 15, include those wherein an inert diluent is used with the dechlorination reaction. In this case, the inert diluent is preferably any material which is in the gas phase under the reaction conditions and which does not react with any component present in the reactor during the dechlorination reaction. The inert diluent may include nitrogen, and the like.
The temperature range for dechlorination may vary depending on the combination of catalyst, haloethane starting material and alkane/alkene. In order to carry out the dechlorination in the gas phase, the temperature and pressure should be such that all the reactants are in the gas phase. Moreover, temperatures equal to or higher than the decomposition temperatures of the reactants and products should be avoided.
Preferred temperatures for the dechlorination reaction are between about 300 ℃ and about 650 ℃, with between about 400 ℃ and about 600 ℃ being more preferred, and between about 450 ℃ and about 600 ℃ being more preferred, and between about 500 ℃ and about 600 ℃ being most preferred. The temperature of the gas phase dechlorination reaction may be above 500 ℃ or above about 550 ℃ and up to about 600 ℃.
The processes of the present invention, including each of processes 1 to 15, include those wherein the contact time is sufficiently long to allow the reactants to react in contact with the catalyst. Accordingly, the processes of the present invention, including each of processes 1 to 15, include those wherein the contact time is from about 1 second to about 6 seconds, with 3 seconds to 5 seconds being more preferred.
The processes of the present invention, including each of processes 1 through 15, include those wherein haloalkanes are produced with good selectivity, particularly those wherein selectivity to haloalkane products is preferably greater than about 75%, or selectivity is preferably greater than about 80%, or selectivity is preferably greater than about 85%, or selectivity is preferably greater than about 90%.
The conversion of the starting haloalkane by the dechlorination process is very good. The conversion is preferably from about 30% to about 95%, or preferably from about 50% to about 95%.
Inventive aspects
Aspect 1: a process for the production of halogenated ethylene, and preferably perhalogenated ethylene, said process comprising the gas-phase dechlorination of a halogenated ethane, preferably a perhalogenated ethane, in the presence of a catalyst, wherein said halogenated ethane or perhalogenated ethane contains at least two chlorine atoms on adjacent carbon atoms, and wherein said catalyst is selected from the group consisting of: (a) transition metal oxides such as iron (III) oxide, nickel (II) oxide, copper (II) oxide and mixtures thereof, and (b) transition metal fluorides and chlorides such as copper (II) chloride and copper (II) fluoride.
Aspect 2: a process for producing a vinyl halide having the formula:
CFmCln＝CFxCly
wherein
m is 0 to 2, n is 0 to 2, and m + n is 2; and is
x is 0 to 2, y is 0 to 2, and x + y is 2;
the process comprises the vapor phase dechlorination of a halogenated ethane having the formula:
CFmCln＝CFxCly
wherein
m is 0 to 2, n is 0 to 2, and m + n is 2; and is
x is 0 to 2, y is 0 to 2, and x + y is 2;
the catalyst is selected from: (a) transition metal oxides such as iron (III) oxide, nickel (II) oxide, copper (II) oxide and mixtures thereof, and (b) transition metal fluorides and chlorides such as copper (II) chloride and copper (II) fluoride.
Aspect 3: a process for the production of halogenated ethylene, and preferably perhalogenated ethylene, which comprises the gas-phase dechlorination of a halogenated ethane, preferably perhalogenated ethane, in the presence of a catalyst and an alkane or alkene, wherein the halogenated ethane or perhalogenated ethane comprises at least two chlorine atoms on adjacent carbon atoms, and wherein the catalyst is selected from the group consisting of: (a) transition metal oxides such as iron (III) oxide, nickel (II) oxide, copper (II) oxide and mixtures thereof, and (b) transition metal fluorides and chlorides such as copper (II) chloride and copper (II) fluoride.
Aspect 4: a process for producing a vinyl halide having the formula:
CFmCln＝CFxCly
wherein
m is 0 to 2, n is 0 to 2, and m + n is 2; and is
x is 0 to 2, y is 0 to 2, and x + y is 2;
the process comprises the vapor phase dechlorination of a halogenated ethane having the formula:
CFmCln＝CFxCly
wherein
m is 0 to 2, n is 0 to 2, and m + n is 2; and is
x is 0 to 2, y is 0 to 2, and x + y is 2;
the catalyst is selected from: (a) transition metal oxides such as iron (III) oxide, nickel (II) oxide, copper (II) oxide and mixtures thereof, and (b) transition metal fluorides and chlorides such as copper (II) chloride and copper (II) fluoride.
Aspect 5: the method of any one of aspects 1 to 4, wherein the catalyst is on a carbon support.
Aspect 6: the method of any one of aspects 1 to 5, wherein the catalyst comprises Fe2O3、NiO、CuO、CuF2、CuCl2And mixtures thereof.
Aspect 7: the method of any one of aspects 1 to 6, wherein the catalyst is selected from carbon-supported Fe2O3/NiO, carbon-supported Fe2O3CuO, carbon-supported CuF2And carbon-supported CuCl2。
Aspect 8: the process of any one of aspects 1 to 7, wherein the dechlorination reaction comprises an alkane having from 1 to 6 carbon atoms, and preferably from 1 to 4 carbon atoms.
Aspect 9: the process of any of aspects 1-8, wherein the dechlorination reaction comprises an alkane selected from the group consisting of: methane, ethane, propane, butane, isobutane, pentane, hexane, cyclopentane and cyclohexane, especially propane.
Aspect 10: the process of any one of aspects 1 to 9, wherein the molar ratio of the haloethane starting material to the alkane is between about 1:1 to about 1:10, with between about 1:1 to about 1:3 being more preferred.
Aspect 11: the process of any one of aspects 1 to 7, wherein the dechlorination reaction comprises an olefin having from 2 to 6 carbon atoms, and preferably from 2 to 4 carbon atoms.
Aspect 12: the process of any of aspects 1-7, wherein the dechlorination reaction comprises an olefin selected from the group consisting of: ethylene, propylene, butene, pentene, cyclopentene, and cyclohexene.
Aspect 13: the process of any of aspects 1-7, 11, or 12, wherein the molar ratio of the haloethane starting material to the alkene is between about 1:1 to about 1:10, with between about 1:1 to about 1:3 being more preferred.
Aspect 14: the process of any one of aspects 1-13, wherein the dechlorination reaction is at a temperature of between about 400 ℃ and about 650 ℃.
Aspect 15: the process of any of aspects 1-13, wherein the dechlorination reaction is at a temperature of between about 450 ℃ and about 600 ℃.
Aspect 16: the process of any of aspects 1-13, wherein the dechlorination reaction is at a temperature of between about 500 ℃ and about 600 ℃.
Aspect 17: the process of any of aspects 1-13, wherein the dechlorination reaction is at a temperature of greater than 500 ℃ or greater than about 550 ℃ and up to about 600 ℃.
Aspect 18: the process of any of aspects 1-17, wherein the dechlorination reaction further comprises a dilution gas.
Aspect 19: the method of aspect 18, wherein the diluent gas comprises nitrogen (N)2) A gas.
Aspect 20: the process of any one of aspects 1-19, wherein the dechlorination reaction provides a haloalkane product with a selectivity of greater than about 75%.
Aspect 21: the process of any one of aspects 1-19, wherein the dechlorination reaction provides a haloalkane product with a selectivity of greater than about 80%.
Aspect 22: the process of any one of aspects 1-19, wherein the dechlorination reaction provides a haloalkane product with a selectivity of greater than about 85%.
Aspect 23: the process of any one of aspects 1-19, wherein the dechlorination reaction provides a haloalkane product with a selectivity of greater than about 90%.
Aspect 24: a process for the production of Chlorotrifluoroethylene (CTFE), the process comprising the gas phase dechlorination of 1,1, 2-trichloro-1, 2, 2-trifluoroethane (CFC-113) in the presence of a catalyst and optionally an alkane or alkene, wherein the catalyst is selected from the group consisting of: (a) transition metal oxides such as iron (III) oxide, nickel (II) oxide, copper (II) oxide and mixtures thereof, and (b) transition metal fluorides and chlorides such as copper (II) chloride and copper (II) fluoride.
Aspect 25: the method of aspect 24, wherein the catalyst is on a carbon support.
Aspect 26: the method of aspect 24 or 25, wherein the catalyst comprises Fe2O3、NiO、CuO、CuF2、CuCl2And mixtures thereof.
Aspect 27: the method of any one of aspects 24 to 26, wherein the catalyst is selected from Fe on carbon2O3/NiO, carbon-supported Fe2O3CuO, carbon-supported CuF2And carbon-supported CuCl2。
Aspect 28: the process of any one of aspects 24 to 27, wherein the dechlorination reaction comprises an alkane having from 1 to 6 carbon atoms, and preferably from 1 to 6 carbon atoms.
Aspect 29: the process of any one of aspects 24 to 28, wherein the dechlorination reaction comprises an alkane selected from the group consisting of: methane, ethane, propane, butane, isobutane, pentane, hexane, cyclopentane and cyclohexane, especially propane.
Aspect 30: the process of any one of aspects 24 to 29, wherein the molar ratio of the CFC-113 starting material to the alkane is between about 1:1 to about 1:10, with between about 1:1 to about 1:3 being preferred.
Aspect 31: the process of any one of aspects 24 to 27, wherein the dechlorination reaction comprises an olefin having from 2 to 6 carbon atoms, and preferably from 2 to 4 carbon atoms.
Aspect 32: the process of any one of aspects 24 to 27, wherein the dechlorination reaction comprises an olefin selected from the group consisting of: ethylene, propylene, butene, pentene, cyclopentene, and cyclohexene.
Aspect 33: the process of any of aspects 24 to 27, 31 or 32, wherein the molar ratio of the CFC-113 starting material to the olefin is between about 1:1 to about 1:10, with between about 1:1 to about 1:3 being preferred.
Aspect 34: the process of any one of aspects 24 to 33, wherein the dechlorination reaction is at a temperature of between about 400 ℃ and about 650 ℃.
Aspect 35: the process of any one of aspects 24 to 33, wherein the dechlorination reaction is at a temperature of between about 450 ℃ and about 600 ℃.
Aspect 36: the process of any one of aspects 24 to 33, wherein the dechlorination reaction is at a temperature of between about 500 ℃ and about 600 ℃.
Aspect 37: the process of any one of aspects 24 to 33, wherein the dechlorination reaction is at a temperature of greater than 500 ℃ or greater than about 550 ℃ and up to about 600 ℃.
Aspect 38: the process of any one of aspects 24-37, wherein the dechlorination reaction further comprises a dilution gas.
Aspect 39: the method of aspect 38, wherein the diluent gas comprises nitrogen (N)2) A gas.
Aspect 40: the process of any one of aspects 24-39, wherein the dechlorination reaction provides a CTFE product with a selectivity of greater than about 75%.
Aspect 41: the process of any one of aspects 24-39, wherein the dechlorination reaction provides a CTFE product with a selectivity of greater than about 80%.
Aspect 42: the process of any one of aspects 24-39, wherein the dechlorination reaction provides a CTFE product with a selectivity of greater than about 85%.
Aspect 43: the process of any one of aspects 24-39, wherein the dechlorination reaction provides a CTFE product with a selectivity of greater than about 90%.
The following non-limiting examples are illustrative of certain embodiments of the present invention and should not be construed as limiting. Variations and additional or alternative embodiments will be apparent to the skilled person based on the disclosure provided herein.