US7230146B2
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US
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Process for producing fluoropropenes
Assignee: Honeywell International Inc
•
Filing: 2003-10-27
•
Granted: 2007-06-12
•
Expires: 2023-10-27
Abstract
Abstract Dehydrohalogenation processes for the preparation of fluoropropenes from corresponding halopropanes, in which the fluoropropenes have the formula CF<SUB>3</SUB>CY-CX<SUB>N</SUB>H<SUB>P</SUB>, wherein X and Y are independently hydrogen or a halogen selected from fluorine, chlorine, bromine and iodine; and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2.
Inventors
- 👤 Daniel C. Merkel
- 👤 Rajiv R. Singh
- 👤 Hsueh Sung Tung
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 09:07
CPC Classifications
C; C07; C07C; C07C21/00; C07C21/02; C07C21/18; C07C17/00; C07C17/093; C07C17/20; C07C17/202; C07C17/206; C07C17/25
Claims Analysis
Total Claims: 83
Claim 1
Independent Claim
184 words
A dehydrohalogenation process for the preparation of fluoropropenes of the formula CF 3 CY═CX N H P , wherein X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine; and N and P are independently integers equal to 0,1 or 2, provided that (N+P)=2; comprising reacting without a catalyst, a halopropane of the formula: CF 3 C(YR 1 )C(X N H P R 2 ) wherein R 1 , R 2 , X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, provided that at least one of R 1 , R 2 , X and Y is a halogen and there is at least one hydrogen and one halogen on adjacent carbon atoms; with a caustic solution of at least one alkali metal or alkaline earth metal hydroxide in a non-aqueous, non-alcohol solvent for said alkali metal or alkaline earth metal hydroxide that is essentially miscible with said halopropane, wherein the reaction is performed within a temperature range at which dehydrohalogenation will occur.
Claim 2
Dependent Claim
184 words
A dehydrohalogenation process for the preparation of fluoropropenes of the formula CF 3 CY═CX N H P , wherein X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine; and N and P are independently integers equal to 0,1 or 2, provided that (N+P)=2; comprising reacting without a catalyst, a halopropane of the formula: CF 3 C(YR 1 )C(X N H P R 2 ) wherein R 1 , R 2 , X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, provided that at least one of R 1 , R 2 , X and Y is a halogen and there is at least one hydrogen and one halogen on adjacent carbon atoms; with a caustic solution of at least one alkali metal or alkaline earth metal hydroxide in a non-aqueous, non-alcohol solvent for said alkali metal or alkaline earth metal hydroxide that is essentially miscible with said halopropane, wherein the reaction is performed within a temperature range at which dehydrohalogenation will occur.
Claim 3
Dependent Claim
10 words
The process of claim 1 wherein the reactant comprises 1-chloro-1,3,3,3-tetrafluoropropane.
Claim 4
Dependent Claim
10 words
The process of claim 1 wherein the reactant comprises 1,1,1,3,3-pentafluoropropane.
Claim 5
Dependent Claim
13 words
The process of claim 1 wherein the reactant comprises both 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,1,3,3-pentafluoropropane.
Claim 6
Dependent Claim
25 words
The process of claim 1 wherein said caustic solution comprises LiOH, NaOH, KOH, CaO, Ca(OH) 2 , CaCO 3 , lime stone or combinations thereof.
Claim 7
Dependent Claim
33 words
The process of claim 1 , wherein said caustic solution solvent is selected from the group consisting of nitriles, ethers, esters, amides, ketones, sulfoxides, phosphates,carboxylates, and combinations of two or more of these.
Claim 8
Dependent Claim
13 words
The process of claim 1 , wherein said caustic solution solvent comprises acetonitrile.
Claim 9
Dependent Claim
14 words
The process of claim 1 , wherein said caustic solution solvent comprises diethyl ether.
Claim 10
Dependent Claim
13 words
The process of claim 1 , wherein said caustic solution solvent comprises tetrahydrofuran.
Claim 11
Dependent Claim
13 words
The process of claim 1 , wherein said caustic solution solvent comprises perfluorotetrahydrofuran.
Claim 12
Dependent Claim
14 words
The process of claim 1 , wherein said caustic solution solvent comprises methyl acetate.
Claim 13
Dependent Claim
14 words
The process of claim 1 , wherein said caustic solution solvent comprises ethyl acetate.
Claim 14
Dependent Claim
20 words
The process of claim 4 wherein said dehydrohalogenation of said 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,1,3,3-pentafluoropropane are conducted simultaneously in the same reactor.
Claim 15
Dependent Claim
22 words
The process of claim 1 wherein the reaction is conducted at a temperature of from about 20° C. to about 150° C.
Claim 16
Dependent Claim
16 words
The process of claim 1 wherein the reaction is conducted at atmospheric pressure or under vacuum.
Claim 17
Dependent Claim
13 words
The process or claim 1 wherein the reaction is conducted at superatmospheric pressure.
Claim 18
Dependent Claim
24 words
The process of claim 1 wherein the caustic strength of said caustic solution is from about 2 wt % to about 100 wt %.
Claim 19
Dependent Claim
20 words
The process of claim 1 , wherein the molar ratio of caustic to halopropane is about 1:1 to about 20:1.
Claim 20
Dependent Claim
35 words
The process of claim 1 wherein the reactant comprises 1-chloro-1,3,3,3-tetrafluoropropane and/or 1,1,1,3,3-pentafluoropropane,and wherein said reactant is previously prepared by fluorinating 1,1,1,3,3-pentachloropropane with hydrogen fluoride in a vapor phase in the presence of a fluorination catalyst.
Claim 21
Dependent Claim
36 words
The process of claim 19 wherein said fluorination catalyst is selected from the group consisting of transition metal halides, Group IVb metal halides, Group Vb metal halides and combinations thereof on activated carbon or fluorinated alumina.
Claim 22
Dependent Claim
100 words
The process of claim 19 wherein said fluorination catalyst is selected from the group consisting of SbCl 5 , SbCl 3 , SbF 5 , TaCl 5 , SnCl 4 , NbCl 5 , TiCl 4 , MoCl 5 , Cr 2 O 3 , Cr 2 O 3 /Al 2 O 3 , Cr 2 O 3 /AlF 3 , Cr 2 O 3 /carbon, CoCl 2 /Cr 2 O 3 /Al 2 O 3 , NiCl 2 /Cr 2 O 3 /Al 2 O 3 , CoCl 2 /AlF 3 , NiCl 2 /AlF 3 and combinations thereof.
Claim 23
Dependent Claim
44 words
The process of claim 19 wherein said fluorination catalyst is selected from the group consisting of Cr 2 O 3 , Cr 2 O 3 /carbon, Cr 2 O 3 /AlF 3 ,CoCl 2 /AlF 3 , NiCl 2 /AlF 3 and combinations thereof.
Claim 24
Dependent Claim
19 words
The process of claim 19 wherein said fluorination catalyst comprises SbCl 3 or SbCl 5 supported on activated carbon.
Claim 25
Dependent Claim
36 words
The process of claim 1 wherein the reactant comprises 1-chloro-1,3,3,3-tetrafluoropropane and/or 1,1,1,3,3-pentafluoropropane, and wherein said reactant is previously prepared by fluorinating 1,1,1,3,3-pentachloropropane with hydrogen fluoride in a liquid phase in the presence of a fluorination catalyst.
Claim 26
Dependent Claim
30 words
The process of claim 24 wherein said fluorination catalyst is selected from the group consisting of transition metal halides, Group IVb metal halides, Group Vb metal halides and combinations thereof.
Claim 27
Dependent Claim
42 words
The process of claim 24 wherein said fluorination catalyst is selected from the group consisting of SbCl 5 , SbCl 3 , SbF 5 , TaCl 5, SnCl 4 , NbCl 5 , TiCl 4 , MoCl 5 , and combinations thereof.
Claim 28
Dependent Claim
24 words
The process of claim 24 wherein said fluorination catalyst is selected from the group consisting of SbCl 5 , SbCl 3 and combinations thereof.
Claim 29
Dependent Claim
22 words
The process of claim 19 wherein the fluorination is conducted at a temperature of from about 100° C. to about 350° C.
Claim 30
Dependent Claim
16 words
The process of claim 19 wherein the fluorination is conducted at atmospheric pressure or under vacuum.
Claim 31
Dependent Claim
21 words
The process of claim 29 , wherein the fluorination is conducted under vacuum pressure between about 5 and about 760 torr.
Claim 32
Dependent Claim
14 words
The process of claim 19 , wherein said fluorination is conducted at superatmospheric pressure.
Claim 33
Dependent Claim
21 words
The process of claim 19 wherein the mole ratio of hydrogen fluoride to 1,1,1,3,3-pentachloropropane is from about 2:1 to about 100:1.
Claim 34
Dependent Claim
19 words
The process of claim 19 further comprising feeding chlorine to the fluorination reaction to keep the fluorination catalyst active.
Claim 35
Dependent Claim
22 words
The process of claim 24 wherein the fluorinating is conducted at a temperature of from about 60° C. to about 180° C.
Claim 36
Dependent Claim
21 words
The process of claim 24 wherein the fluorinating is conducted at a pressure of from about 50 psig and 400 psig.
Claim 37
Dependent Claim
21 words
The process of claim 24 wherein the mole ratio of hydrogen fluoride to 1,1,1,3,3-pentachloropropane is from about 2:1 to about 100:1.
Claim 38
Dependent Claim
19 words
The process of claim 24 further comprising feeding chlorine to the fluorination reaction to keep the fluorination catalyst active.
Claim 39
Dependent Claim
150 words
A dehydrohalogenation process for the preparation of fluoropropenes of the formula CF 3 CY═CX N H P , wherein X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2; comprising heating to a temperature at which dehydrohalogenation by thermal decomposition occurs, a halopropane of the formula: CF 3 C(YR 1 )C(X N H P R 2 ) wherein R 1 , R 2 , X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, provided that at least one of R 1 , R 2 , X and Y is a halogen and there is at least one hydrogen and one halogen on adjacent carbon atoms; wherein said decomposing is conducted without a catalyst.
Claim 40
Dependent Claim
150 words
A dehydrohalogenation process for the preparation of fluoropropenes of the formula CF 3 CY═CX N H P , wherein X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2; comprising heating to a temperature at which dehydrohalogenation by thermal decomposition occurs, a halopropane of the formula: CF 3 C(YR 1 )C(X N H P R 2 ) wherein R 1 , R 2 , X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, provided that at least one of R 1 , R 2 , X and Y is a halogen and there is at least one hydrogen and one halogen on adjacent carbon atoms; wherein said decomposing is conducted without a catalyst.
Claim 41
Dependent Claim
47 words
A process for the manufacture of 1,3,3,3-tetrafluoropropene comprising thermally decomposing a reactant comprising at least one of 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropane, under conditions sufficient to dehyd rochlorinate 1-chloro-1,3,3,3-tetrafluoropropane and/or to dehydrofluorinate 1,1,1,3,3-pentafluoropropane, to form a reaction product which comprises 1,3,3,3-tetrafluoropropene; wherein said decomposing is conducted without a catalyst.
Claim 42
Dependent Claim
47 words
A process for the manufacture of 1,3,3,3-tetrafluoropropene comprising thermally decomposing a reactant comprising at least one of 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropane, under conditions sufficient to dehyd rochlorinate 1-chloro-1,3,3,3-tetrafluoropropane and/or to dehydrofluorinate 1,1,1,3,3-pentafluoropropane, to form a reaction product which comprises 1,3,3,3-tetrafluoropropene; wherein said decomposing is conducted without a catalyst.
Claim 43
Dependent Claim
71 words
A process for the manufacture of 1,3,3,3-tetrafluoropropene comprising thermally decomposing a reactant comprising at least one of 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropane, under conditions sufficient to dehydrochlorinate 1-chloro-1,3,3,3-tetrafluoropropane and/or to dehydrofluorinate 1,1,1,3,3-pentafluoropropane, to form a reaction product which comprises 1,3,3,3-tetrafluoropropene; wherein said decomposing is conducted in the presence of one or more transition metal halide catalysts, wherein said transition metal is selected from the group consisting of iron, nickel, cobalt, and combinations thereof.
Claim 44
Dependent Claim
71 words
A process for the manufacture of 1,3,3,3-tetrafluoropropene comprising thermally decomposing a reactant comprising at least one of 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropane, under conditions sufficient to dehydrochlorinate 1-chloro-1,3,3,3-tetrafluoropropane and/or to dehydrofluorinate 1,1,1,3,3-pentafluoropropane, to form a reaction product which comprises 1,3,3,3-tetrafluoropropene; wherein said decomposing is conducted in the presence of one or more transition metal halide catalysts, wherein said transition metal is selected from the group consisting of iron, nickel, cobalt, and combinations thereof.
Claim 45
Dependent Claim
24 words
The process of claim 40 , the catalyst is selected from, a group consisting of iron halides, nickel halides, cobalt halides and combinations thereof.
Claim 46
Dependent Claim
17 words
The process of claim 39 wherein 1-chloro-1,3,3,3-tetrafluoropropane is dehydrochlorinated to form a reaction product which comprises 1,3,3,3-tetrafluoropropene.
Claim 47
Dependent Claim
17 words
The process of claim 39 wherein 1,1,3,3,3-pentafluoropropane is dehydrofluorinated to form a reaction product which comprises 1,3,3,3-tetrafluoropropene.
Claim 48
Dependent Claim
22 words
The process of claim 39 wherein said dehydrochlorination of 1-chloro-1,3,3,3-tetrafluoropropane and said dehydrofluorination of 1,1,1,3,3,-pentafluoropropane are conducted simultaneously in the same reactor.
Claim 49
Dependent Claim
20 words
The process of claim 39 which is conducted at a temperature of from about 30° C. to about 400° C.
Claim 50
Dependent Claim
20 words
The process of claim 39 which is conducted at a temperature of from about 50° C. to about 350° C.
Claim 51
Dependent Claim
20 words
The process of claim 39 which is conducted at a temperature of from about 75° C. to about 300° C.
Claim 52
Dependent Claim
14 words
The process of claim 39 which is conducted at atmospheric pressure or under vacuum.
Claim 53
Dependent Claim
11 words
The process of claim 39 which is conducted a superatmospheric pressure.
Claim 54
Dependent Claim
172 words
A dehydrohalogenation process for the preparation of fluoropropenes of the formula CF 3 CY═CX N H P , wherein X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2; comprising heating to a temperature at which dehydrohalogenation by thermal decomposition occurs, a halopropane of the formula: CF 3 C(YR 1 )C(X N H P R 2 ) wherein R 1 , R 2 , X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, provided that least one of R 1 , R 2 , X and Y is a halogen and there is at least one hydrogen and one halogen on adjacent carbon atoms; wherein said decomposing is conducted in the presence of a transition metal halide catalyst wherein said transition metal is selected from the group consisting of iron, nickel, cobalt, and combinations thereof.
Claim 55
Dependent Claim
172 words
A dehydrohalogenation process for the preparation of fluoropropenes of the formula CF 3 CY═CX N H P , wherein X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2; comprising heating to a temperature at which dehydrohalogenation by thermal decomposition occurs, a halopropane of the formula: CF 3 C(YR 1 )C(X N H P R 2 ) wherein R 1 , R 2 , X and Y are independently hydrogen or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, provided that least one of R 1 , R 2 , X and Y is a halogen and there is at least one hydrogen and one halogen on adjacent carbon atoms; wherein said decomposing is conducted in the presence of a transition metal halide catalyst wherein said transition metal is selected from the group consisting of iron, nickel, cobalt, and combinations thereof.
Claim 56
Dependent Claim
15 words
The process of claim 50 wherein the catalyst is supported or bulk transition metal halides.
Claim 57
Dependent Claim
23 words
The process of claim 51 wherein said catalyst comprises supported or bulk FeCl 2 , FeCl 3 , NiCl 2 or CoCl 2.
Claim 58
Dependent Claim
30 words
The process of claim 39 wherein the 1-chloro-1,3,3,3-tetrafluoropropane and/or 1,1,1,3,3-pentafluoropropane are previously prepared by fluorinating 1,1,1,3,3-pentachloropropane with hydrogen fluoride in the vapor phase in the presence of a fluorination catalyst.
Claim 59
Dependent Claim
36 words
The process of claim 53 wherein said fluorination catalyst is selected from the group consisting of transition metal halides, Group IVb metal halides, Group Vb metal halides and combinations thereof on activated carbon or fluorinated alumina.
Claim 60
Dependent Claim
100 words
The process of claim 53 wherein said fluorination catalyst is selected from the group consisting of SbCl 5 , SbCl 3 , SbF 5 , TaCl 5 , SnCl 4 , NbCl 5 , TiCl 4 , MoCl 5 , Cr 2 O 3 , Cr 2 O 3 /Al 2 O 3 , Cr 2 O 3 /AlF 3 , Cr 2 O 3 carbon, CoCl 2 /Cr 2 O 3 /Al 2 O 3 , NiCl 2 /Cr 2 O 3 /Al 2 O 3 , CoCl 2 /AlF 3 , NiCl 2 /AlF 3 and combinations thereof.
Claim 61
Dependent Claim
45 words
The process of claim 53 wherein said fluorination catalyst is selected from the group consisting of Cr 2 O 3 , Cr 2 O 3 /carbon, Cr 2 O 3 /AlF 3 , CoCl 2 /AlF 3 , NiCl 2 /AlF 3 and combinations thereof.
Claim 62
Dependent Claim
19 words
The process of claim 53 wherein said fluorination catalyst comprises SbCl 3 or SbCl 5 supported on activated carbon.
Claim 63
Dependent Claim
22 words
The process of claim 53 wherein the fluorinating is conducted at a temperature of from about 100° C. to about 350° C.
Claim 64
Dependent Claim
16 words
The process of claim 53 wherein the fluorinating is conducted at atmospheric pressure or under vacuum.
Claim 65
Dependent Claim
13 words
The process of claim 53 wherein the fluorinating is conducted at superatmospheric pressure.
Claim 66
Dependent Claim
21 words
The process of claim 53 wherein the mole ratio of hydrogen fluoride to 1,1,1,3,3-pentachloropropane is from about 2:1 to about 100:1.
Claim 67
Dependent Claim
19 words
The process of claim 53 further comprising feeding chlorine to the fluorinating reaction to keep the fluorination catalyst active.
Claim 68
Dependent Claim
30 words
The process of claim 39 wherein the 1-chloro-1,3,3,3-tetrafluoropropane and/or 1,1,1,3,3-pentafluoropropane are previously prepared by fluorinating 1,1,1,3,3-pentachloropropane with hydrogen fluoride in a liquid phase in the presence of a fluorination catalyst.
Claim 69
Dependent Claim
30 words
The process of claim 63 wherein said fluorination catalyst is selected from the group consisting of transition metal halides, Group IVb metal halides, Group Vb metal halides and combinations thereof.
Claim 70
Dependent Claim
43 words
The process of claim 64 wherein said fluorination catalyst is selected from the group consisting of SbCl 5 , SbCl 3 , SbF 5 , TaCl 5 , SnCl 4 , NbCl 5 , TiCl 4 , MoCl 5 , and combinations thereof.
Claim 71
Dependent Claim
24 words
The process of claim 65 wherein said fluorination catalyst is selected from the group consisting of SbCl 5 , SbCl 3 and combinations thereof.
Claim 72
Dependent Claim
22 words
The process of claim 63 wherein the fluorinating is conducted at a temperature of from about 60° C. to about 180° C.
Claim 73
Dependent Claim
21 words
The process of claim 63 wherein the fluorinating is conducted at a pressure of from about 50 psig and 400 psig.
Claim 74
Dependent Claim
21 words
The process of claim 63 wherein the mole ratio of hydrogen fluoride to 1,1,1,3,3-pentachloropropane is from about 2:1 to about 100:1.
Claim 75
Dependent Claim
19 words
The process of claim 63 further comprising feeding chlorine to the fluorinating reaction to keep the fluorination catalyst active.
Claim 76
Dependent Claim
33 words
The process of claim 1 , wherein said caustic solution further comprises a 1 to 5 carbon atom alcohol in an amount that is at least partially miscible with said caustic solution solvent.
Claim 77
Dependent Claim
27 words
The process of claim 1 , wherein said caustic solution further comprises water in an amount that is at least partially miscible with said caustic solution solvent.
Claim 78
Dependent Claim
11 words
The process of claim 1 , conducted in a continuous manner.
Claim 79
Dependent Claim
15 words
The process of claim 38 , wherein said process is conducted in a continuous manner.
Claim 80
Dependent Claim
46 words
A process for the manufacture of 1,3,3,3-tetrafluoropropene comprising thermally decomposing substantially simultaneously a reactant comprising 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropane under conditions sufficient to dehydrochlorinate at least a portion of said 1-chloro-1,3,3,3-tetrafluoropropane and to dehydrofluorinate at least a portion of 1,1,1,3,3-pentafluoropropane, to form a reaction product comprising 1,3,3,3-tetrafluoropropene.
Claim 81
Dependent Claim
46 words
A process for the manufacture of 1,3,3,3-tetrafluoropropene comprising thermally decomposing substantially simultaneously a reactant comprising 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropane under conditions sufficient to dehydrochlorinate at least a portion of said 1-chloro-1,3,3,3-tetrafluoropropane and to dehydrofluorinate at least a portion of 1,1,1,3,3-pentafluoropropane, to form a reaction product comprising 1,3,3,3-tetrafluoropropene.
Claim 82
Dependent Claim
45 words
A process for the manufacture of 1,3,3,3-tetrafluoropropene comprising thermally decomposing in the presence of a catalyst a reactant comprising at least one of 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropane under conditions sufficient to dehydrohalogenate at least a portion of said reactant to form a reaction product comprising 1,3,3,3-tetrafluoropropene.
Claim 83
Dependent Claim
45 words
A process for the manufacture of 1,3,3,3-tetrafluoropropene comprising thermally decomposing in the presence of a catalyst a reactant comprising at least one of 1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropane under conditions sufficient to dehydrohalogenate at least a portion of said reactant to form a reaction product comprising 1,3,3,3-tetrafluoropropene.
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