Systems and methods for producing z-1, 1, 1, 4, 4, 4-hexafluoro-2-butene

Abstract

Systems and methods for the preparation of (Z)-1, 1, 1, 4, 4, 4-hexafluoro-2-butene are provided. Compositions prepared according to one or more of the systems and methods described herein and methods of using these compositions are also provided.

Description

Technical Field

[0001] This disclosure generally relates to methods for synthesizing fluorinated olefins. More specifically, the present invention relates to methods and intermediates for preparing (Z)-1,1,1,4,4,4-hexafluoro-2-butene, and compositions that can be used as fire extinguishing agents / flame suppressants, propellants, foaming agents, solvents, cleaning fluids, and / or immersion cooling fluids in applications including refrigerants, high-temperature heat pumps, and organic Rankine cycles. Background Technology

[0002] For decades, the fluorocarbon industry has been striving to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out under the Montreal Protocol. Solutions for many applications involve the commercialization of hydrofluorocarbon (HFC) compounds used as refrigerants, solvents, fire extinguishing agents, foaming agents, and propellants. These currently most widely used new compounds (such as HFC refrigerants, HFC-134a, and HFC-125) have zero ozone depletion potential and are therefore unaffected by the current Montreal Protocol phase-out provisions.

[0003] Besides ozone depletion, global warming is another environmental concern for many of these applications. Therefore, compositions that meet both low ozone depletion criteria and low global warming potential are needed. Certain hydrofluoroolefins are believed to meet both objectives. Therefore, there is a need to provide a method for manufacturing hydrofluoroolefins with low global warming potential.

[0004] (Z)-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) is an example of such a hydrofluoroolefin. This invention provides an economical system and method for producing Z-HFO-1336mzz from hexachlorobutadiene (HCBD).

[0005] HCBD is primarily produced in chlorination units as a byproduct of carbon tetrachloride and tetrachloroethylene production. Chlorination is a free radical chain reaction that occurs when hydrocarbons are exposed to chlorine gas under pyrolysis conditions. The hydrocarbons are chlorinated, and the resulting chlorinated hydrocarbons are decomposed. The process is similar to combustion, but with chlorine instead of oxygen.

[0006] Carbon tetrachloride and tetrachloroethylene are both commodities manufactured on such a large scale that sufficient HCBD is usually available to meet industrial demands. Therefore, HCBD can constitute a low-cost and readily available starting material for providing manufacturing methods for halogenated hydrocarbons and fluoroolefins.

[0007] Furthermore, as a byproduct of carbon tetrachloride and tetrachloroethylene production, HCBD constitutes waste that must be disposed of to prevent environmental pollution. Therefore, the manufacturing method of the present invention utilizes HCBD as a starting material for the production of hydrofluoroolefins, transforming potentially environmentally polluting waste into an environmentally friendly product. Summary of the Invention

[0008] Any embodiment of the invention discussed herein may be used alone or in combination with each other. Those skilled in the art will understand that the different embodiments discussed herein can be combined and form part of this invention. Those skilled in the art will also understand that certain aspects of the different embodiments discussed herein can be combined and form part of this invention.

[0009] In one embodiment, the present invention relates to a system for purifying E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz). The system comprises: a reactor configured to react hexachlorobutadiene (HCBD) with hydrofluoric acid (HF) in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD, and unreacted HF; and a first distillation column configured to receive the composition from the reactor and configured to separate the first composition into a first fraction F1 containing HCl. D10 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D10 The second distillation column is configured to receive a second fraction F2 from the first distillation column, comprising unreacted HCBD, unreacted HF, and HCFO-1326 mmol / L. D10 It is configured to separate the second fraction into a third fraction F3 containing an azeotrope of unreacted HF and HCFO-1326mxz. D11 And the fourth fraction F4, which contains unreacted HCBD, unreacted HF, and HCFO-1326mxz. D11 The second distillation column is optionally configured to distill the third fraction F3. D11 The product is returned to the reactor; and to the third distillation column, which is configured to receive a fourth fraction F4 from the second distillation column, comprising unreacted HCBD, unreacted HF, and HCFO-1326 MXZ. D11 And is configured to deliver the fourth fraction F4 D11 The fifth fraction, F5, was separated into unreacted HF and unreacted HCBD. D12 And the sixth fraction F6 containing HCFO-1326mxz D12 The third distillation column is optionally configured to distill the fifth fraction F5. D12Return to the reactor.

[0010] In one embodiment, the present invention relates to a system for purifying E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz). The system comprises: a reactor configured to react hexachlorobutadiene (HCBD) with hydrofluoric acid (HF) in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD, and unreacted HF; and a first distillation column configured to receive the composition from the reactor and configured to separate the first composition into a first fraction F1 containing HCl. D20 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D20 The second distillation column is configured to receive a second fraction F2 from the first distillation column, comprising unreacted HCBD, unreacted HF, and HCFO-1326 mmol / L. D20 And is configured to transfer the second fraction F2 D20 The third fraction, F3, was separated into unreacted HF and unreacted HCBD. D21 And the fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz. D21 The second distillation column is optionally configured to distill the third fraction F3. D21 Returning to the reactor; and the acid neutralizer, which is configured to receive the fourth fraction F4, containing an azeotrope of HF and HCFO-1326mxz, from the second distillation column. D21 And is configured to deliver the fourth fraction F4 D21 Separated into the fifth fraction F5, which contains neutralized HF. A20 And the sixth fraction F6 containing HCFO-1326mxz A20 .

[0011] In one embodiment, the present invention relates to a system for purifying hexafluoro-2-butyne (HFB). The system comprises: a reactor configured to react E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) with a base comprising an alkali metal hydroxide in the presence of a phase transfer catalyst to form a composition comprising a vapor portion and a liquid portion, the vapor portion comprising HFB and HCFO-1326mxz, the liquid portion comprising water, HCFO-1326mxz, an excess of the phase transfer catalyst, and an alkali metal halide salt, the liquid portion consisting of an aqueous liquid phase and an organic liquid phase; and a distillation column configured to receive the vapor portion of the composition from the reactor and configured to separate the vapor portion into a fraction F5 containing HFB.D31 And fraction F6 containing HCFO-1326mxz D31 The distillation column is configured to distill the fraction F6 containing HCFO-1326mxz. D31 Returning to the reactor, the distillation column is optionally configured to deliver fraction F5 containing HFB. D31 Provided to one or more additional distillation columns.

[0012] In one embodiment, the present invention relates to a system for purifying cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). The system comprises: a reactor configured to react hexafluoro-2-butyne (HFB) with hydrogen in the presence of a hydrogenation catalyst to form a composition comprising HFO-1336mzz(Z) and HFB; and a first distillation column configured to receive the composition from the reactor and configured to separate the composition into a first fraction F1 comprising HFB. D40 and the second fraction F2 containing HFO-1336mzz(Z) D40 The first distillation column is configured to distill the first fraction F1. D40 Return to the reactor.

[0013] In one embodiment, the present invention relates to a method for purifying E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz). The method comprises: reacting hexachlorobutadiene (HCBD) with hydrofluoric acid (HF) in a reactor in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD, and unreacted HF; providing the composition to a first distillation column and separating the composition into a first fraction F1 containing HCl. D10 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D10 The second fraction F2 from the first distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326 mg / z, is... D10 The fraction is fed to a second distillation column, where it is separated into a third fraction, F3, containing an azeotrope of unreacted HF and HCFO-1326mxz. D11 And the fourth fraction F4, which contains unreacted HCBD, unreacted HF, and HCFO-1326mxz. D11 ;Optionally, the third fraction F3 D11 The product is returned to the reactor from the second distillation column; the fourth fraction F4 from the second distillation column contains unreacted HCBD, unreacted HF, and HCFO-1326 MXZ. D11It is supplied to the third distillation column, and the fourth fraction F4 is distilled. D11 The fifth fraction, F5, was separated into unreacted HF and unreacted HCBD. D12 And the sixth fraction F6 containing HCFO-1326mxz D12 ; and optionally the fifth fraction F5 D12 It returns to the reactor from the third distillation column.

[0014] In one embodiment, the present invention relates to a method for purifying E- and / or Z-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz). The method comprises: reacting hexachlorobutadiene (HCBD) with hydrofluoric acid (HF) in a reactor in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD, and unreacted HF; providing the composition from the reactor to a first distillation column; and separating the first composition into a first fraction F1 containing HCl. D20 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D20 The second fraction F2 from the first distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326 mg / z, is... D20 The second distillation column is supplied with the second fraction F2. D20 The third fraction, F3, was separated into unreacted HF and unreacted HCBD. D21 And the fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz. D21 ;Optionally, the third fraction F3 D21 The product is returned to the reactor from the second distillation column; and the fourth fraction F4, containing the azeotrope of HF and HCFO-1326mxz from the second distillation column, is also returned. D21 It is supplied to an acid neutralizer, which is configured to neutralize the fourth fraction F4. D21 Separated into the fifth fraction F5, which contains neutralized HF. A20 And the sixth fraction F6 containing HCFO-1326mxz A20 .

[0015] In one embodiment, the present invention relates to a method for purifying hexafluoro-2-butyne (HFB). The method comprises: reacting E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) with a base comprising an alkali metal hydroxide in a reactor in the presence of a phase transfer catalyst to form a composition comprising a vapor portion and a liquid portion, the vapor portion comprising HFB and unreacted HCFO-1326mxz, the liquid portion comprising water, unreacted HCFO-1326mxz, excess phase transfer catalyst, and an alkali metal halide salt, the liquid portion consisting of an aqueous liquid phase and an organic liquid phase; providing the vapor portion of the composition from the reactor to one or more distillation columns, and separating the vapor portion into a fraction F5 containing HFB. D31 And fraction F6 containing unreacted HCFO-1326mxz D31 ; and optionally, fraction F6 containing unreacted HCFO-1326mxz. D31 It returns from the distillation column to the reactor.

[0016] Implementation Scheme 1: A system for purifying E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), said system comprising:

[0017] A reactor configured to react hexachlorobutadiene (HCBD) with hydrofluoric acid (HF) in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD, and unreacted HF.

[0018] A first distillation column is configured to receive the composition from the reactor and to separate the first composition into a first fraction F1 containing HCl. D10 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D10 ;

[0019] A second distillation column is configured to receive, from the first distillation column, a second fraction F2 comprising unreacted HCBD, unreacted HF, and HCFO-1326mxz. D10 And configured to separate the second fraction into a third fraction F3 containing an azeotrope of unreacted HF and HCFO-1326mxz. D11 And the fourth fraction F4, which contains unreacted HCBD, unreacted HF, and HCFO-1326mxz. D11 The second distillation column is optionally configured to distill the third fraction F3. D11 Return to the reactor; and

[0020] A third distillation column is configured to receive the fourth fraction F4, comprising unreacted HCBD, unreacted HF, and HCFO-1326mxz, from the second distillation column. D11 And is configured to deliver the fourth fraction F4 D11 The fifth fraction, F5, was separated into unreacted HF and unreacted HCBD. D12 And the sixth fraction F6 containing HCFO-1326mxz D12 The third distillation column is optionally configured to distill the fifth fraction F5. D12 Return to the reactor.

[0021] Implementation Scheme 2: The system according to Implementation Scheme 1, wherein the first fraction F1 D10Contains HCl, HF, and one or more additional compounds selected from the group consisting of: (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E-HCFO-1326mxz); (E)-(2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) (E-CFO-1317mx); (Z)- (2-Chloro-1,1,1,3,4,4,4-Hepanofluoro-2-butene) (Z-CFO-1317mx); 2-Chloro-1,1-difluoroethylene (HCFC-1122); 2-Chloro-1,1,1,2-tetrafluoroethane (HCFC-124); fluoropentachloroethane (CFC-111); 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114); 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113); 2-Chloro-1,1,1 - Trifluoroethane (CFC-133a); 2,2-Dichloro-1,1,1-trifluoroethane (CFC-123); 1,2-Dichloro-1,1,2-trifluoroethane (CFC-123a); 1,2,2-Trichloro-1,1-difluoroethane (CFC-122); 1,1,1,2-Tetrachloro-2,2-difluoroethane (CFC-112a); 1,1,1,3-Tetrafluoro-2,3,3-trichloropropane (HCFC-224db); 1,2-Dichloro-1,1,3-trifluoroethane 3,3-Pentafluoropropane (HCFC-225da); 2,3-Dichloro-1,1,1,3-Tetrafluoropropane (HCFC-234da); 2-Chloro-1,1,1,3,3-Pentafluoropropane (HCFC-235da); 1-Chloro-1,1,3,3,3-Pentafluoropropane (CFC-235fa); 1,1,1,3,3,3-Hexafluoropropane (HFC-236fa) and 1,1,1,2,4,4,4-Hepanofluoro-2-butene (HFO-1327mz).

[0022] Implementation Scheme 3: The system according to Implementation Scheme 2, wherein based on the first fraction F1 D10 The total weight of the HF is about 1% or less by weight, or about 0.5% or less by weight, or about 0.1% or less by weight.

[0023] Implementation Scheme 4: The system according to Implementation Scheme 2, wherein based on the first fraction F1 D10 The total weight present in the first fraction F1 D10 Each of the additional compounds is present in an amount of about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less.

[0024] Implementation Scheme 5: The system according to Implementation Scheme 2, wherein based on the first fraction F1 D10 The total weight of the first fraction F1 D10 The total amount of the additional compounds is about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less.

[0025] Implementation Scheme 6: The system according to Implementation Scheme 1, wherein the sixth fraction F6 D12 Include:

[0026] (i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz);

[0027] (ii) Optional HF; and

[0028] (iii) One or more additional compounds, said additional compounds being selected from the group consisting of:

[0029] E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene,

[0030] E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0031] Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0032] HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene)

[0033] HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene),

[0034] HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene),

[0035] HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0036] HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0037] HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane)

[0038] HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane)

[0039] HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane)

[0040] HFC-356mff (1,1,1,4,4,4-hexafluorobutane)

[0041] HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane)

[0042] HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane)

[0043] HCFC-1122 (2-chloro-1,1-difluoroethylene)

[0044] HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane)

[0045] CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane)

[0046] CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane)

[0047] CFC-133a (2-chloro-1,1,1-trifluoroethane)

[0048] CFC-123 (2,2-dichloro-1,1,1-trifluoroethane)

[0049] CFC-123a (1,2-dichloro-1,1,2-trifluoroethane)

[0050] CFC-122 (1,2,2-trichloro-1,1-difluoroethane)

[0051] CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane),

[0052] HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane)

[0053] HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane)

[0054] HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane)

[0055] HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane)

[0056] HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and

[0057] E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

[0058] Implementation Scheme 7: The system according to Implementation Scheme 1, wherein the sixth fraction F6 D12 It comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); optional HF; and one or more additional compounds selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), E-Z-CFO-1317mx (E-2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) and Z-CFO-1317mx (Z-2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

[0059] Implementation Scheme 8: The system according to any one of Implementation Schemes 6 and 7, alone or in any combination thereof, wherein the sixth fraction F6 is based on... D12 The total weight of the HF is about 1% or less by weight, or about 0.5% or less by weight, or about 0.1% or less by weight.

[0060] Implementation Scheme 9: A system for purifying E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), said system comprising:

[0061] A reactor configured to react hexachlorobutadiene (HCBD) with hydrofluoric acid (HF) in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD, and unreacted HF.

[0062] A first distillation column is configured to receive the composition from the reactor and to separate the first composition into a first fraction F1 containing HCl. D20 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D20 ;

[0063] A second distillation column is configured to receive, from the first distillation column, a second fraction F2 comprising unreacted HCBD, unreacted HF, and HCFO-1326mxz. D20 And configured to transfer the second fraction F2 D20The third fraction, F3, was separated into unreacted HF and unreacted HCBD. D21 And the fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz. D21 The second distillation column is optionally configured to distill the third fraction F3. D21 Return to the reactor; and

[0064] An acid neutralizer configured to receive the fourth fraction F4, comprising an azeotrope of HF and HCFO-1326mxz, from the second distillation column. D21 And is configured to deliver the fourth fraction F4 D21 Separated into the fifth fraction F5, which contains neutralized HF. A20 And the sixth fraction F6 containing HCFO-1326mxz A20 .

[0065] Implementation Scheme 10: The system according to Implementation Scheme 9, wherein the first fraction F1 D20It comprises HCl, HF, and one or more additional compounds selected from the group consisting of: (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); (E)-2-chloro-1,1,1,4,4,34-hexafluoro-2-butene (E-HCFO-1326mxz); (E)-(2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) (E-CFO-1317mx); (Z) -(2-Chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) (Z-CFO-1317mx); 2-Chloro-1,1-difluoroethylene (HCFC-1122); 2-Chloro-1,1,1,2-tetrafluoroethane (HCFC-124); fluoropentachloroethane (CFC-111); 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114); 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113); 2-Chloro-1,1,1 - Trifluoroethane (CFC-133a); 2,2-Dichloro-1,1,1-trifluoroethane (CFC-123); 1,2-Dichloro-1,1,2-trifluoroethane (CFC-123a); 1,2,2-Trichloro-1,1-difluoroethane (CFC-122); 1,1,1,2-Tetrachloro-2,2-difluoroethane (CFC-112a); 1,1,1,3-Tetrafluoro-2,3,3-trichloropropane (HCFC-224db); 1,2-Dichloro-1,1,3-trifluoroethane 3,3-Pentafluoropropane (HCFC-225da); 2,3-Dichloro-1,1,1,3-Tetrafluoropropane (HCFC-234da); 2-Chloro-1,1,1,3,3-Pentafluoropropane (HCFC-235da); 1-Chloro-1,1,3,3,3-Pentafluoropropane (CFC-235fa); 1,1,1,3,3,3-Hexafluoropropane (HFC-236fa) and 1,1,1,2,4,4,4-Hepanofluoro-2-butene (HFO-1327mz).

[0066] Implementation Scheme 11: The system according to Implementation Scheme 10, wherein based on the first fraction F1 D20 The total weight of the HF is about 1% or less by weight, or about 0.5% or less by weight, or about 0.1% or less by weight.

[0067] Implementation Scheme 12: The system according to Implementation Scheme 10, wherein based on the first fraction F1 D20 The total weight present in the first fraction F1 D20 Each of the additional compounds is present in an amount of about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less.

[0068] Implementation Scheme 13: The system according to Implementation Scheme 10, wherein based on the first fraction F1 D20 The total weight of the first fraction F1 D20 The total amount of the additional compounds is about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less.

[0069] Implementation Scheme 14: The system according to Implementation Scheme 9, wherein the sixth fraction F6 A20 Include

[0070] (i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz);

[0071] (ii) Optional HF; and

[0072] (iii) One or more additional compounds, said additional compounds being selected from the group consisting of:

[0073] E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene,

[0074] E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0075] Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0076] HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene)

[0077] HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene),

[0078] HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene),

[0079] HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0080] HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0081] HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane)

[0082] HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane)

[0083] HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane)

[0084] HFC-356mff (1,1,1,4,4,4-hexafluorobutane)

[0085] HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane)

[0086] HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane)

[0087] HCFC-1122 (2-chloro-1,1-difluoroethylene)

[0088] HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane)

[0089] CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane)

[0090] CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane)

[0091] CFC-133a (2-chloro-1,1,1-trifluoroethane)

[0092] CFC-123 (2,2-dichloro-1,1,1-trifluoroethane)

[0093] CFC-123a (1,2-dichloro-1,1,2-trifluoroethane)

[0094] CFC-122 (1,2,2-trichloro-1,1-difluoroethane)

[0095] CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane),

[0096] HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane)

[0097] HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane)

[0098] HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane)

[0099] HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane)

[0100] HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and

[0101] E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

[0102] Implementation Scheme 15: The system according to Implementation Scheme 9, wherein the sixth fraction F6 A20 Include

[0103] (i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz);

[0104] (ii) Optional HF; and

[0105] (iii) One or more additional compounds selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), E-Z-CFO-1317mx (E-2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) and Z-CFO-1317mx (Z-2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

[0106] Implementation Scheme 16: The system according to Implementation Scheme 15, wherein based on the sixth fraction F6 A20 The total weight of the HF is about 1% or less by weight, or about 0.5% or less by weight, or about 0.1% or less by weight.

[0107] Implementation Scheme 17: The system according to any one of Implementation Schemes 1 to 16, alone or in any combination thereof, wherein the system further includes a partial condenser coupled to the reactor.

[0108] Implementation Scheme 18: A system for purifying hexafluoro-2-butyne (HFB), the system comprising:

[0109] A reactor configured to react E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) with a base comprising an alkali metal hydroxide in the presence of a phase transfer catalyst to form a composition comprising a vapor portion and a liquid portion, the vapor portion comprising HFB and HCFO-1326mxz, the liquid portion comprising water, HCFO-1326mxz, excess phase transfer catalyst and alkali metal halide salt, the liquid portion consisting of an aqueous liquid phase and an organic liquid phase;

[0110] A distillation column configured to receive the vapor portion of the composition from the reactor and configured to separate the vapor portion into a fraction F5 containing HFB. D31 And fraction F6 containing HCFO-1326mxz D31 The distillation column is configured to distill the fraction F6 containing HCFO-1326mxz. D31 Returning to the reactor, the distillation column is optionally configured to return the fraction F5 containing HFB. D31 Provided to one or more additional distillation columns.

[0111] Implementation Scheme 19: The system according to Implementation Scheme 18, wherein the system further includes a portion of the condenser connected to the reactor.

[0112] Implementation Scheme 20: The system according to any one of Implementation Schemes 17 to 18, alone or in any combination thereof, wherein the fraction F6 D31 Include:

[0113] (i)HCFO-1326mxz、

[0114] (ii) One or more compounds selected from the group consisting of trifluoroacetone, trifluoropropyne, and hexafluoro-2-butyne, and

[0115] (iii) One or more of the additional compounds selected from the following groups:

[0116] E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene,

[0117] E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0118] Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0119] HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene)

[0120] HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene),

[0121] HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene),

[0122] HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0123] HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0124] HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane)

[0125] HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane)

[0126] HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane)

[0127] HFC-356mff (1,1,1,4,4,4-hexafluorobutane)

[0128] HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane)

[0129] HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane)

[0130] HCFC-1122 (2-chloro-1,1-difluoroethylene)

[0131] HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane)

[0132] CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane)

[0133] CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane)

[0134] CFC-133a (2-chloro-1,1,1-trifluoroethane)

[0135] CFC-123 (2,2-dichloro-1,1,1-trifluoroethane)

[0136] CFC-123a (1,2-dichloro-1,1,2-trifluoroethane)

[0137] CFC-122 (1,2,2-trichloro-1,1-difluoroethane)

[0138] CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane),

[0139] HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane)

[0140] HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane)

[0141] HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane)

[0142] HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane)

[0143] HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and

[0144] E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

[0145] Implementation Scheme 21: The system according to any one of Implementation Schemes 18 to 20, alone or in any combination thereof, wherein the fraction F6 D31 The water content is approximately 5000 ppm or less, or approximately 4000 ppm or less, or approximately 3000 ppm or less, or approximately 1000 ppm or less.

[0146] Implementation Scheme 22: The system according to any one of Implementation Schemes 18 to 22, alone or in any combination thereof, further includes:

[0147] A decanter, configured to receive the liquid portion of the composition from the reactor, and configured to separate the aqueous liquid phase into a first fraction F1 comprising water and the alkali metal halide salt. E30 The organic liquid phase was then separated into a second fraction, F2, containing unreacted HCFO-1326mxz and excess phase transfer catalyst. E30 The decanter is configured to decan the second fraction F2 E30 The first portion is returned to the reactor; and

[0148] An additional distillation column, configured to receive the second fraction F2 from the decanter. E30 The second part, and configured to deliver the second fraction F2 E30 The second part was separated into a third fraction F3 containing unreacted HCFO-1326mxz. D30 And the fourth fraction F4, which contains unreacted HCFO-1326mxz and excess PTC. D30 The additional distillation column is configured to distill the third fraction F3 containing unreacted HCFO-1326mxz. D30 Return to the reactor.

[0149] Implementation Scheme 23: The system according to Implementation Scheme 22, wherein the third fraction F3 D30 Include:

[0150] (i)HCFO-1326mxz、

[0151] (ii)(ii) one or more of trifluoroacetone and hexafluoro-2-butyne, and

[0152] (iii) One or more of the additional compounds selected from the following groups:

[0153] E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene,

[0154] E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0155] Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0156] HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene)

[0157] HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene),

[0158] HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene),

[0159] HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0160] HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0161] HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane)

[0162] HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane)

[0163] HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane)

[0164] HFC-356mff (1,1,1,4,4,4-hexafluorobutane)

[0165] HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane)

[0166] HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane)

[0167] HCFC-1122 (2-chloro-1,1-difluoroethylene)

[0168] HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane)

[0169] CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane)

[0170] CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane)

[0171] CFC-133a (2-chloro-1,1,1-trifluoroethane)

[0172] CFC-123 (2,2-dichloro-1,1,1-trifluoroethane)

[0173] CFC-123a (1,2-dichloro-1,1,2-trifluoroethane)

[0174] CFC-122 (1,2,2-trichloro-1,1-difluoroethane)

[0175] CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane),

[0176] HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane)

[0177] HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane)

[0178] HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane)

[0179] HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane)

[0180] HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and

[0181] E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

[0182] Implementation Scheme 24: The system according to any one of Implementation Schemes 22 to 23, alone or in any combination thereof, wherein the third fraction F3 D30 It contains approximately 100 ppm or less of the base.

[0183] Implementation Scheme 25: The system according to any one of Implementation Schemes 22 to 24, alone or in any combination thereof, wherein the third fraction F3 D30 It contains approximately 500 ppm or less of the phase transfer catalyst.

[0184] Implementation Scheme 26: A system for purifying cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), the system comprising:

[0185] A reactor configured to react hexafluoro-2-butyne (HFB) with hydrogen in the presence of a hydrogenation catalyst to form a composition comprising HFO-1336mzz(Z) and HFB; and

[0186] A first distillation column is configured to receive the composition from the reactor and to separate the composition into a first fraction F1 containing HFB. D40 and the second fraction F2 containing HFO-1336mzz(Z) D40 The first distillation column is configured to distill the first fraction F1 D40 Return to the reactor.

[0187] Implementation Scheme 27: The system according to Implementation Scheme 26, wherein the reactor contains a thermal diluent, preferably selected from the group consisting of HFC-32, HFC-143a, HFC-134a and HFC-134.

[0188] Implementation Scheme 28: The system according to any one of Implementation Schemes 26 to 27, alone or in any combination thereof, further includes a second distillation column configured to receive the second fraction F2 from the first distillation column. D40 And is configured to transfer the second fraction F2 D40 The third fraction, F3, was separated into HFO-1336mzz(Z), HFO-1336mzz(E), 1,1,4,4,4-hexafluorobutane (HCFC-356mff), and lower-boiling organic byproducts from the hydrogenation reaction. D41 And the fourth fraction F4, which contains HFO-1336mzz(Z) and higher-boiling organic byproducts from the hydrogenation reaction. D41 The system optionally further includes a third distillation column configured to receive the fourth fraction F4 from the second distillation column. D41 And is configured to deliver the fourth fraction F4 D41 Separation into the first fraction F5 containing Z-HFO-1336mzzD42 And a second fraction F6 containing Z-HFO-1336mzz and higher-boiling organic byproducts from the hydrogenation reaction. D42 .

[0189] Implementation Scheme 29: An integrated system for preparing Z-HFO-1336mzz from HCBD, said integrated system comprising the system according to Implementation Schemes 1 to 8, or the system according to Implementation Schemes 9 to 17, and the systems according to Implementation Schemes 18 to 25 and Implementation Schemes 26 to 28, individually or in any combination thereof.

[0190] Implementation Scheme 30: The integrated system according to Implementation Scheme 29, wherein the third distillation column of the system according to Implementation Schemes 1 to 8 is configured to distill the sixth fraction F6 containing HCFO-1326mxz. D12 The system is supplied to the dehydrochlorination reactor of the system according to embodiments 18 to 25, wherein the distillation column of the system according to embodiments 18 to 5 is configured to deliver the seventh fraction F7 containing HFB. D32 The hydrogenation reactors supplied to the systems described in embodiments 26 to 28, individually or in any combination thereof.

[0191] Implementation Scheme 31: The integrated system according to Implementation Scheme 29, wherein the acid neutralizer A20 of the system according to Implementation Schemes 9 to 17 is configured to contain the sixth fraction F6 containing HCFO-1326mxz. A20 The system is supplied to the dehydrochlorination reactor of the system according to embodiments 18 to 25, wherein the distillation column of the system according to embodiments 18 to 25 is configured to deliver the seventh fraction F7 containing HFB. D32 The hydrogenation reactors supplied to the systems described in embodiments 2 to 28, individually or in any combination thereof.

[0192] Implementation Scheme 32: A method for purifying E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), the method comprising:

[0193] Hexachlorobutadiene (HCBD) is reacted with hydrofluoric acid (HF) in a reactor in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD and unreacted HF.

[0194] The composition is fed to a first distillation column, and the composition is separated into a first fraction F1 containing HCl. D10And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D10 ;

[0195] The second fraction F2 from the first distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326mxz, is... D10 The fraction is fed to a second distillation column, where it is separated into a third fraction, F3, containing an azeotrope of unreacted HF and HCFO-1326mxz. D11 And the fourth fraction F4, which contains unreacted HCBD, unreacted HF, and HCFO-1326mxz. D11 ;

[0196] Optionally, the third fraction F3 D11 Return from the second distillation column to the reactor;

[0197] The fourth fraction F4 from the second distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326mxz, is... D11 The fourth fraction F4 is supplied to the third distillation column. D11 The fifth fraction, F5, was separated into unreacted HF and unreacted HCBD. D12 And the sixth fraction F6 containing HCFO-1326mxz D12 ;as well as

[0198] Optionally, the fifth fraction F5 D12 The product is returned from the third distillation column to the reactor.

[0199] Implementation Scheme 33: A method for purifying E- and / or Z-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), the method comprising:

[0200] Hexachlorobutadiene (HCBD) is reacted with hydrofluoric acid (HF) in a reactor in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD and unreacted HF.

[0201] The composition from the reactor is provided to a first distillation column, and the first composition is separated into a first fraction F1 containing HCl. D20 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D20 ;

[0202] The second fraction F2 from the first distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326mxz, is... D20 The second fraction F2 is supplied to the second distillation column. D20 The third fraction, F3, was separated into unreacted HF and unreacted HCBD. D21 And the fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz. D21 ;

[0203] Optionally, the third fraction F3 D21 Return from the second distillation column to the reactor; and

[0204] The fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz, from the second distillation column. D21 Provided to an acid neutralizer, the acid neutralizer being configured to neutralize the fourth fraction F4 D21 Separated into the fifth fraction F5, which contains neutralized HF. A20 And the sixth fraction F6 containing HCFO-1326mxz A20 .

[0205] Implementation Scheme 34: A method for purifying hexafluoro-2-butyne (HFB), the method comprising:

[0206] In the presence of a phase transfer catalyst, E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) is reacted with a base containing an alkali metal hydroxide in a reactor to form a composition comprising a vapor portion and a liquid portion, wherein the vapor portion comprises HFB and unreacted HCFO-1326mxz, and the liquid portion comprises water, unreacted HCFO-1326mxz, excess phase transfer catalyst, and an alkali metal halide salt, wherein the liquid portion consists of an aqueous liquid phase and an organic liquid phase;

[0207] The vapor fraction of the composition from the reactor is provided to one or more distillation columns, and the vapor fraction is separated into a fraction F5 containing HFB. D31 And fraction F6 containing unreacted HCFO-1326mxz D31 ;as well as

[0208] Optionally, the fraction F6 containing unreacted HCFO-1326mxz is included. D31 The product is returned from the distillation column to the reactor.

[0209] Implementation Scheme 35: The method according to Implementation Scheme 34 further includes:

[0210] The liquid portion of the composition from the reactor is provided to a decanter, and the aqueous liquid phase is separated into a first fraction F1 containing water and the alkali metal halide salt. E30 The organic liquid phase is then separated into a second fraction, F2, containing the unreacted HCFO-1326mxz and an excess of phase transfer catalyst. E30 ;

[0211] Optionally, the second fraction F2 E30 The first portion returns from the decanter to the reactor;

[0212] The second fraction F2 from the decanter E30 The second portion is provided to an additional distillation column, and the second fraction F2 is... E30 The second part was separated into a third fraction F3 containing unreacted HCFO-1326mxz. D30 And the fourth fraction F4, which contains unreacted HCFO-1326mxz and excess PTC. D30 ;as well as

[0213] Optionally, the third fraction F3 containing unreacted HCFO-1326mxz is included. D30 The distillation column returns the material to the reactor.

[0214] Implementation Scheme 36: A method for purifying cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), the method comprising:

[0215] In the presence of a hydrogenation catalyst, hexafluoro-2-butyne (HFB) is reacted with hydrogen in a reactor to form a composition comprising HFO-1336mzz(Z) and unreacted HFB.

[0216] The composition from the reactor is provided to a first distillation column, and the composition is separated into a first fraction F1 containing unreacted HFB. D40 and the second fraction F2 containing HFO-1336mzz(Z) D40 ;as well as

[0217] Optionally, the first fraction F1 D40 It returns from the first distillation column to the reactor.

[0218] Implementation Scheme 37: The method according to Implementation Scheme 36, the method further includes taking the second fraction F2 from the first distillation column. D40 It is supplied to the second distillation column, and the second fraction F2 is... D40The third fraction, F3, was separated into HFO-1336mzz(Z), HFO-1336mzz(E), 1,1,4,4,4-hexafluorobutane (HCFC-356mff), and lower-boiling organic byproducts from the hydrogenation reaction. D41 And the fourth fraction F4, which contains HFO-1336mzz(Z) and higher-boiling organic byproducts from the hydrogenation reaction. D41 .

[0219] Implementation Scheme 38: An integrated method for purifying Z-HFO-1336mzz from HCBD, the integrated method comprising the methods according to Implementation Schemes 32 and 34 through 37, individually or in any combination thereof, wherein the integrated method comprises purifying the sixth fraction F6 containing HCFO-1326mzz from the third distillation column of the method according to Implementation Scheme 32. D12 Provided to the dehydrochlorination reactor according to embodiment 34, and the seventh fraction F7 containing HFB from the distillation column according to embodiment 34. D32 Provided to the hydrogenation reactor according to the method of embodiment 36.

[0220] Implementation Scheme 39: An integrated method for purifying Z-HFO-1336mzz from HCBD, the integrated method comprising the methods according to Implementation Schemes 33 to 37, individually or in any combination thereof, the integrated method comprising purifying the sixth fraction F6 containing HCFO-1326mxz from the acid neutralizer A20 according to the method of Implementation Scheme 33. A20 Provided to the dehydrochlorination reactor according to embodiment 34, and the seventh fraction F7 containing HFB from the distillation column according to embodiment 34. D32 Provided to the hydrogenation reactor according to the method of embodiment 36.

[0221] Implementation Scheme 40: A composition prepared by any one of the systems according to Embodiments 1 to 17 or by any one of the methods according to Embodiments 32 to 33, alone or in any combination thereof, the composition comprising:

[0222] i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and

[0223] ii) Selected from one or more of the following additional compounds:

[0224] 1,1,1,3,3,3-Hexafluoropropane;

[0225] 1,1,1,2,2,4,4,4-octafluorobutane;

[0226] 1,1,1,4,4,4-Hexafluorobutane;

[0227] 1,2-Dichloro-1,1,2,2-Tetrafluoroethane;

[0228] 2-Chloro-1,1,1-trifluoroethane;

[0229] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0230] 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane;

[0231] 2-Chloro-1,1,1,3,3-pentafluoropropane;

[0232] 1-Chloro-1,1,3,3,3-pentafluoropropane;

[0233] (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0234] 1,2-Dichloro-3,3,4,4-Tetrafluorocyclobut-1-ene;

[0235] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane;

[0236] 2,2-Dichloro-1,1,1-trifluoroethane;

[0237] 1,2-Dichloro-1,1,2-trifluoroethane;

[0238] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane;

[0239] (E)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0240] 1,1,2-Trichloro-1,2,2-trifluoroethane;

[0241] (Z)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0242] 1,2-Dichloro-3,3,3-trifluoroprop-1-ene;

[0243] (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene;

[0244] 2,2-Dichloro-1,1,1,4,4,4-hexafluorobutane;

[0245] dl-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane;

[0246] Meso-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane;

[0247] 1,2-Dichloro-3,3,4,4,4-pentafluorobut-1-ene;

[0248] 2,3-Dichloro-1,1,1,3-Tetrafluoropropane;

[0249] 1,2-Dichloro-1,1,2,4,4,4-hexafluorobutane;

[0250] 1,2,2-Trichloro-1,1-Difluoroethane;

[0251] 1,1,1-Trichloro-2,2-difluoroethane;

[0252] 1,1,2,2-Tetrachloro-1,2-difluoroethane;

[0253] 1,1,1,2-Tetrachloro-2,2-difluoroethane;

[0254] 1,2,3-trichloro-1,1,4,4,4-pentafluorobutane; and

[0255] 1,1,2,3-Tetrachloro-4,4,4-trifluorobut-1-ene,

[0256] The composition contains more than about 95 mol% of Z-HCFO-1326mxz.

[0257] Embodiment 41: A composition prepared by a system according to any one of Embodiments 18 to 25 or a method according to any one of Embodiments 34 to 35, alone or in any combination thereof, the composition comprising:

[0258] i) Hexafluorobutyne (HFB); and

[0259] ii) One or more additional compounds, said additional compounds being selected from the group consisting of:

[0260] 1,1,1,3,3,3-Hexafluoropropane;

[0261] 1,1,1,2,4,4,4-Hepenofluoro-2-butene;

[0262] (E)-1,1,1,4,4,4-hexafluorobutene;

[0263] 1,1,1,2,2,4,4,4-octafluorobutane;

[0264] 1,1,1,4,4,4-Hexafluorobutane;

[0265] 1,2-Dichloro-1,1,2,2-Tetrafluoroethane;

[0266] 2-Chloro-1,1,1-trifluoroethane;

[0267] (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0268] 1-Chloro-3,3,4,4,4-pentafluorobut-1-yne;

[0269] 1-Chloro-3,3,4,4,4-pentafluorobut-2-yne;

[0270] (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene;

[0271] 1,2-Dichloro-3,3,4,4,4-pentafluorobut-1-ene;

[0272] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0273] 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane;

[0274] 2-Chloro-1,1,1,3,3-pentafluoropropane;

[0275] 1-Chloro-1,1,3,3,3-pentafluoropropane;

[0276] (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0277] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane;

[0278] 2,2-Dichloro-1,1,1-trifluoroethane;

[0279] 1,2-Dichloro-1,1,2-trifluoroethane;

[0280] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane;

[0281] (E)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0282] 1,1,2-Trichloro-1,2,2-trifluoroethane;

[0283] (Z)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0284] 1-Chloro-3,3,3-trifluoroprop-1-yne;

[0285] 1,2-Dichloro-3,3,3-trifluoroprop-1-ene;

[0286] (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene;

[0287] 1-Chloro-1,1,2,4,4,4-hexafluoro-2-butene;

[0288] 2-Chloro-1,3,3,3-Tetrafluoroprop-1-ene;

[0289] 1,1,3,3,3-pentafluoroprop-1-ene; and

[0290] 2-Chloro-1,1,3,3,3-pentafluoroprop-1-ene,

[0291] The composition contains more than about 95 mol% HFB.

[0292] Implementation Scheme 42: A composition prepared by a system according to any one of Implementation Schemes 26 to 31 or a method according to any one of Implementation Schemes 36 to 39, alone or in any combination thereof, the composition comprising:

[0293] i)(Z)-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz); and

[0294] ii) One or more additional compounds, said additional compounds being selected from:

[0295] 1,1,1,3,3,3-Hexafluoropropane;

[0296] (E)-1,1,1,4,4,4-hexafluorobutene;

[0297] 1,1,1,2,2,4,4,4-octafluorobutane;

[0298] 1,2-Dichloro-1,1,2,2-Tetrafluoroethane;

[0299] 3-Chloro-1,1,1-trifluoropropane;

[0300] 4-Chloro-1,1,1,2,2-pentafluorobutane;

[0301] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0302] 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane;

[0303] 2-Chloro-1,1,1,3,3-pentafluoropropane;

[0304] 1-Chloro-1,1,3,3,3-pentafluoropropane;

[0305] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane;

[0306] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane;

[0307] 1,2-Dichloro-3,3,3-trifluoroprop-1-ene;

[0308] 1-Chloro-3,3,3-trifluoropropene;

[0309] 1-Chloro-1,1,2,4,4,4-hexafluoro-2-butene;

[0310] 1-Chloro-1,1,4,4,4-pentafluorobutane;

[0311] 2-Chloro-1,1,1,3-Tetrafluoropropane; and

[0312] 1,1,1,3,3-Pentafluoropropane,

[0313] The composition contains more than about 99 mol% of Z-HFO-1336mzz. Attached Figure Description

[0314] The following detailed description of preferred embodiments of the invention will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the invention, presently preferred embodiments are shown in the drawings. However, it should be understood that the invention is not limited to the precise arrangements and means shown. In the drawings:

[0315] Figure 1 A schematic diagram of a system and method for producing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene from hexachlorobutadiene according to one embodiment of the present invention;

[0316] Figure 2 A schematic diagram of a system and method for producing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene from hexachlorobutadiene according to another embodiment of the present invention;

[0317] Figure 3 A schematic diagram of a system and method for producing hexafluoro-2-butyne from 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene according to one embodiment of the present invention; and

[0318] Figure 4 This is a schematic diagram of a system and method for producing (Z)-1,1,1,4,4,4-hexafluoro-2-butene from hexafluoro-2-butyne according to one embodiment of the present invention. Detailed Implementation

[0319] This invention generally relates to methods, intermediates, and compositions for the preparation of (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

[0320] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, conditions A or B satisfy one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0321] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If in a claim, it will not include protection for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claim.

[0322] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect one or more essential and novel features of the invention protected by the claims, particularly the mode of action for achieving the desired results of any of the methods of the invention. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0323] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0324] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. This description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0325] As used herein, the term “about” is intended to account for variations due to experimental error (e.g., adding or subtracting approximately 10% of the indicated value). Unless otherwise expressly stated, all measurements reported herein should be understood to be modified by the term “about,” whether or not the term is explicitly used.

[0326] When quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually. Wherever a numerical range is given herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0327] As used herein, the term "compound" means all stereoisomers, geometric isomers, tautomers, and isotopes that include the structure or chemical described. Unless otherwise stated, compounds identified herein by name or structure as a particular tautomer are intended to include other tautomers.

[0328] As used in this article, the term "catalyst" refers to a substance that accelerates a chemical reaction but is not consumed by the reaction; therefore, it can be recovered without undergoing a chemical change at the end of the reaction.

[0329] This invention discloses a method for preparing cis-1,1,1,4,4,4-hexafluoro-2-butene, the method comprising: fluorinating hexachlorobutadiene (HCBD) in the presence of a catalyst to obtain a first product mixture containing E- or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E- or Z-HCFO-1326mxz); recovering E- or Z-HCFO-1326mxz, such as by subjecting the first product mixture to one or more separation steps to provide E- or Z-HCFO-1326mxz; and in the presence of an alkali metal hydroxide... In the presence of a phase transfer catalyst, E- or Z-HCFO-1326mxz is dehydrochlorinated in an alkaline environment to produce a second product mixture containing hexafluoro-2-butyne (HFB); HFB is recovered, such as by subjecting the second product mixture to one or more separation steps to provide hexafluoro-2-butyne; HFB is hydrogenated in the presence of a hydrogenation catalyst to produce a third reaction mixture containing Z-HFO-1336mzz; and Z-HFO-1336mzz is recovered, such as by subjecting the third product mixture to one or more separation steps to provide Z-HFO-1336mzz.

[0330] The reaction of this method is as follows:

[0331]

[0332] The present invention also discloses a system for preparing Z-HFO-1336mzz, the system comprising a first reactor for fluorinating HCBD to produce E- or Z-HCFO-1326mxz, a second reactor for dehydrochlorinating E- or Z-HCFO-1326mxz to produce HFB, and a third reactor for hydrogenating HFB to produce Z-HFO-1336mzz.

[0333] Those skilled in the art will understand that for each reaction or process step, the system may include more than one reactor. For example, the system may include multiple first reactors for fluorinating HCBD to produce E- or Z-HCFO-1326mxz, multiple second reactors for dehydrochlorinating E- or Z-HCFO-1326mxz to produce HFB, and / or multiple third reactors for hydrogenating HFB to produce Z-HFO-1336mzz. Each of the multiple first reactors, multiple second reactors, and multiple third reactors may be used in parallel or alternately, for example, when one reactor is offline, another reactor may be online for production.

[0334] The present invention also discloses a system for preparing Z-HFO-1336mzz, the system comprising a first reactor for fluorinating HCBD to produce E- or Z-HCFO-1326mxz, a first group of one or more distillation columns for separating and recovering E- or Z-HCFO-1326mxz, a second reactor for dehydrochlorinating E- or Z-HCFO-1326mxz to produce HFB, a second group of one or more distillation columns for separating and recovering HFB, a third reactor for hydrogenating HFB to produce Z-HFO-1336mzz, and a third group of one or more distillation columns for separating and recovering Z-HFO-1336mzz.

[0335] This document also discloses a method comprising fluorinating HCBD in the presence of a catalyst to produce E- or Z-HCFO-1326mxz. The invention further relates to a system for fluorinating HCBD to produce E- or Z-HCFO-1326mxz, the system comprising a reactor for the fluorination reaction and one or more distillation columns for separating and recovering E- or Z-HCFO-1326mxz, wherein optionally a stream recovered from one or more of these distillation columns is returned to the fluorination reactor. In one embodiment, the system may further include an acid neutralizer and one or more dryers.

[0336] This document also discloses a method comprising dehydrochlorinating E- or Z-HCFO-1326mxz in a base containing an alkali metal hydroxide in the presence of a phase transfer catalyst to produce HFB. The invention also relates to a system for dehydrochlorinating E- or Z-HCFO-1326mxz to produce HFB, the system comprising a reactor for the dehydrochlorination reaction, one or more decanters, and one or more distillation columns for separating and recovering HFB, wherein optionally a stream recovered from one or more of these distillation columns is returned to the dehydrochlorination reactor. In one embodiment, the system for dehydrochlorinating E- or Z-HCFO-1326mxz to produce HFB further includes one or more dryers. For example, the system may include an aluminum-containing adsorbent such as a molecular sieve, preferably an aluminosilicate molecular sieve (zeolite) such as zeolite A, and more particularly molecular sieves selected from zeolite 3A, zeolite 4A, and zeolite 5A.

[0337] This document also discloses a method comprising hydrogenating HFB in the presence of a hydrogenation catalyst to produce Z-HFO-1336mzz. The invention further relates to a system for fluorinating HFB to produce Z-HFO-1336mzz, the system comprising a reactor for the hydrogenation reaction and one or more distillation columns for separating and recovering Z-HFO-1336mzz, wherein optionally a stream recovered from one or more of these distillation columns is returned to the hydrogenation reactor.

[0338] In some embodiments, the system further includes one or more dryers or adsorbents, such as adsorption beds. In one embodiment, the adsorption bed may be in the form of a solid porous core containing zeolite, a binder, and any auxiliary dryer or adsorbent such as silica gel, calcium sulfate, alumina, or activated carbon. In use, the core is contained within a cylinder, and a circulating refrigeration fluid is passed through the cylinder, and the method involves passing a liquid or gaseous composition through the cylinder in contact with the core (i.e., a molecular sieve) to remove acids, trace impurities, etc.

[0339] Systems and Methods

[0340] System A and Method 1, Implementation Scheme 1

[0341] Figure 1 A schematic diagram of a system and method for producing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) from HCBD according to one embodiment of the present invention is shown. Figure 1As shown, a preferred embodiment of the system includes a reactor R10, a first distillation column D10 in flow communication with the reactor R10, a second distillation column D11 in flow communication with the first distillation column D10 and the reactor R10, and a third distillation column D12 in flow communication with the second distillation column D11 and the reactor R10.

[0342] refer to Figure 1 HCBD is introduced into reactor R10 via feed stream F10. Anhydrous hydrogen fluoride (HF) is introduced into reactor R10 via feed stream F11. In some embodiments, an oxidant may be fed into reactor R10 via feed stream F12. Those skilled in the art will understand that an oxidant is not required in all cases. In R10, HCBD is fluorinated in the presence of a catalyst containing a catalytically effective amount to produce a product mixture containing E- and Z-HCFO-1326mxz. The reaction is as follows:

[0343]

[0344] In some embodiments, the fluorination process is carried out by flowing HF, HCBD, and an optional oxidant into reactor R10 at a specified temperature. In some embodiments, the process is carried out by flowing HF, HCBD, an optional oxidant such as Cl2, and a carrier gas into the reactor. Examples of carrier gases include inert gases such as nitrogen, argon, and helium.

[0345] The desired reaction results can be achieved by appropriately selecting operating conditions such as temperature, contact time, and the ratio of HF to HCBD.

[0346] The reaction temperature for the catalytic fluorination of HCBD is in the range of about 80°C to about 150°C, or about 80°C to about 140°C. In some embodiments, the process is carried out at a temperature of about 90°C to about 135°C. By maintaining the reaction temperature within these ranges, the formation of byproducts can be reduced, and catalyst deactivation can be suppressed. However, those skilled in the art will understand that the catalytic fluorination of HCBD is an exothermic reaction, and temperatures exceeding about 150°C may locally occur within the reactor R10 or within the catalyst.

[0347] The contact time (CT) between reactants and catalyst in reactor R10 is determined by the following equation:

[0348] ,

[0349] Where VR is the volume (m³) of reactor R10 in cubic meters. 3 ), and VF is the total liquid volumetric flow rate of the reactor feed (m). 3 / hr). In one embodiment, the contact time is in the range of about 0.1 to about 10 hours, including all values ​​and ranges therein. Those skilled in the art will understand that contact time can affect the selectivity and conversion rate of HCBD, and therefore the contact time can be adjusted as needed to a target time in the range of about 0.1 hours to about 10 hours, or to a target time shorter or longer than that range, to achieve the desired reaction results.

[0350] The reaction in reactor R10 is typically carried out at atmospheric pressure, or at a pressure below atmospheric pressure, or at a pressure above atmospheric pressure. That is, the reaction pressure in reactor R10 for the fluorination reaction is not critical and can be adjusted as needed to achieve the desired reaction results. In one embodiment, the catalytic fluorination reaction in reactor R10 is carried out at a pressure above atmospheric pressure, for example, because the increased pressure would reduce the size of the equipment used for the reaction. In one embodiment, the pressure within reactor R10 is in the range of about 0 MPaG to 2.0 MPaG (gauge pressure).

[0351] The reaction mixture obtained in reactor R10 exits reactor R10 as a first feed stream S10 and is supplied to the first distillation column D10 to remove unreacted material and impurities. The reaction mixture (i.e., the first feed stream S10) comprises, or is substantially composed of, unreacted HCBD (standard boiling point 213°C to 215°C), HCFO-1326mxz (standard boiling point 35°C to 43°C), unreacted HF (standard boiling point 20°C), and hydrogen chloride (HCl) (standard boiling point -85°C). HCl is formed as a product of the fluorination reaction of HCBD and HF in reactor R10.

[0352] In some implementations, the first distillation column D10 operates at a pressure of about 300 psig or less, or about 200 psig or less.

[0353] The first distillation column D10 separates the first feed stream S10 into a first fraction containing HCl and impurities, substantially composed of or consisting of HCl, and a second fraction containing HCBD, HF, and HCFO-1326mxz, substantially composed of or consisting of HCBD, HF, and HCFO-1326mxz. The first fraction is removed from the first distillation column D10 in the second feed stream S11. The second fraction is removed from the first distillation column D10 in the third feed stream S12.

[0354] More specifically, the second feed stream S11 (i.e., the first fraction) comprises, substantially comprises, or comprises: HCl, optionally trace amounts of HF, and optionally one or more additional compounds selected from: (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E-HCFO-1326mxz); (E)-(2-chloro-1,1,1,3,4,4,4-hexafluoro-2-butene) (2-Fluoro-2-butene) (E-CFO-1317mx); (Z)-(2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) (Z-CFO-1317mx); 2-chloro-1,1-difluoroethylene (HCFC-1122); 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124); fluoropentachloroethane (CFC-111); 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114); 1,1,2-trichloro-1,2,2-trifluoroethane (C FC-113); 2-chloro-1,1,1-trifluoroethane (CFC-133a); 2,2-dichloro-1,1,1-trifluoroethane (CFC-123); 1,2-dichloro-1,1,2-trifluoroethane (CFC-123a); 1,2,2-trichloro-1,1-difluoroethane (CFC-122); 1,1,1,2-tetrachloro-2,2-difluoroethane (CFC-112a); 1,1,1,3-tetrafluoro-2,3,3-trichloropropane (HCFC-224db); 1,2-di... Chloro-1,1,3,3,3-pentafluoropropane (HCFC-225da); 2,3-dichloro-1,1,1,3-tetrafluoropropane (HCFC-234da); 2-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235da); 1-chloro-1,1,3,3,3-pentafluoropropane (CFC-235fa); 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) and 1,1,1,2,4,4,4-heptafluoro-2-butene (HFO-1327mz).

[0355] In some implementations, based on the total weight of the first fraction, trace amounts of HF account for about 1% or less by weight, or about 0.5% or less by weight, or about 0.1% or less by weight.

[0356] In some embodiments, each additional compound in the first fraction (stream S11) may be present in an amount of about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less, based on the total weight of the first fraction.

[0357] In some embodiments, the total amount of additional compounds in the first fraction (stream S11) is about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less, based on the total weight of the first fraction.

[0358] In some embodiments, the second fraction of the third feed stream S12 comprises HCBD, HF, HCFO-1326mxz, and optionally trace amounts of HCl, substantially or entirely thereof. In some embodiments, the trace amounts of HCl account for about 0.1% by weight or less, or about 0.05% by weight or less, or about 0.02% by weight or less, based on the total weight of the first fraction.

[0359] A third feed stream S12 is then supplied from the first distillation column D10 to the second distillation column D11 to remove unreacted material and impurities. In some embodiments, the second distillation column D11 operates at a pressure of about 200 psig or lower, or about 150 psig or lower, or about 100 psig or lower. The second distillation column D11 separates the third feed stream S12 by distillation into a first fraction consisting of an azeotrope of HF and HCFO-1326 MXZ, substantially composed of or consisting of therein, and a second fraction consisting of HCBD, HF, and HCFO-1326 MXZ, substantially composed of or consisting of therein. The first fraction is removed from the second distillation column D11 in a fourth feed stream S13, and the second fraction is removed from the second distillation column D11 in a fifth feed stream S14.

[0360] A fourth feed stream S13, containing an azeotrope of HF and HCFO-1326mxz, or consisting essentially of or composed of it, is returned or recycled from the second distillation column D11 to reactor R10 for further conversion of HF.

[0361] A fifth feed stream S14, comprising or consisting substantially of HCBD, HF, and HCFO-1326mxz, is supplied to a third distillation column D12 to remove unreacted material and impurities. In some embodiments, the third distillation column D12 operates at a pressure of about 200 psig or lower, or about 150 psig or lower, or about 100 psig or lower. The third distillation column D12 separates the fifth feed stream S14 by distillation into a first fraction comprising or consisting substantially of HF and HCBD, and a second fraction comprising or consisting substantially of HCFO-1326mxz. The first fraction is removed from the third distillation column D12 in a sixth feed stream S15, and the second fraction is removed from the third distillation column D12 in a seventh feed stream S16.

[0362] The seventh feed stream S16 comprises, is substantially composed of, or is composed of HCFO-1326mxz. In some embodiments, the seventh feed stream S16 comprises, is substantially composed of, or is composed of:

[0363] i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz);

[0364] ii) optional trace amounts of HF; and

[0365] iii) Selected from one or more of the following additional compounds:

[0366] E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene,

[0367] E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0368] Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0369] HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene)

[0370] HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene),

[0371] HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene),

[0372] HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0373] HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0374] HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane)

[0375] HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane)

[0376] HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane)

[0377] HFC-356mff (1,1,1,4,4,4-hexafluorobutane)

[0378] HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane)

[0379] HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane)

[0380] HCFC-1122 (2-chloro-1,1-difluoroethylene)

[0381] HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane)

[0382] CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane)

[0383] CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane)

[0384] CFC-133a (2-chloro-1,1,1-trifluoroethane)

[0385] CFC-123 (2,2-dichloro-1,1,1-trifluoroethane)

[0386] CFC-123a (1,2-dichloro-1,1,2-trifluoroethane)

[0387] CFC-122 (1,2,2-trichloro-1,1-difluoroethane)

[0388] CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane),

[0389] HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane)

[0390] HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane)

[0391] HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane)

[0392] HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane)

[0393] HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and

[0394] E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

[0395] In some embodiments, the composition contains more than about 95 mol% of Z-HCFO-1326mxz.

[0396] The one or more additional compounds in the composition containing Z-HCFO-1326mxz are selected from those listed in Table 1.

[0397]

[0398] In some embodiments, the seventh feed stream S16 comprises, substantially comprises, or comprises: Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; optionally, trace amounts of HF; and one or more additional compounds selected from: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene). In some embodiments, the composition comprises greater than about 95 mol% of Z-HCFO-1326mxz.

[0399] In some embodiments, the seventh feed stream S16 comprises, substantially comprises, or comprises: Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane) and optionally trace amounts of HF, wherein the composition comprises greater than about 95 mol% of Z-HCFO-1326mxz, or greater than about 96 mol% of Z-HCFO-1326mxz and greater than about 97 mol% of Z-HCFO-1 326mxz, greater than about 98 mol% of Z-HCFO-1326mxz, greater than about 99 mol% of Z-HCFO-1326mxz, greater than about 99.2 mol% of Z-HCFO-1326mxz, greater than about 99.5 mol% of Z-HCFO-1326mxz, greater than about 99.7 mol% of Z-HCFO-1326mxz, or greater than about 99.9 mol% of Z-HCFO-1326mxz, with the balance being HCFC-336mdd and optional HF.

[0400] In some implementations, the seventh flow S16 comprises, is substantially composed of, or is composed of:

[0401] i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0402] ii) optional trace amounts of HF; and

[0403] iii) Selected from one or more of the following additional compounds:

[0404] 1,1,1,3,3,3-Hexafluoropropane;

[0405] 1,1,1,2,2,4,4,4-octafluorobutane;

[0406] 1,1,1,4,4,4-Hexafluorobutane;

[0407] 1,2-Dichloro-1,1,2,2-Tetrafluoroethane;

[0408] 2-Chloro-1,1,1-trifluoroethane;

[0409] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0410] 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane;

[0411] 2-Chloro-1,1,1,3,3-pentafluoropropane;

[0412] 1-Chloro-1,1,3,3,3-pentafluoropropane;

[0413] (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0414] 1,2-Dichloro-3,3,4,4-Tetrafluorocyclobut-1-ene;

[0415] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane;

[0416] 2,2-Dichloro-1,1,1-trifluoroethane;

[0417] 1,2-Dichloro-1,1,2-trifluoroethane;

[0418] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane;

[0419] (E)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0420] 1,1,2-Trichloro-1,2,2-trifluoroethane;

[0421] (Z)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0422] 1,2-Dichloro-3,3,3-trifluoroprop-1-ene;

[0423] (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene;

[0424] 2,2-Dichloro-1,1,1,4,4,4-hexafluorobutane;

[0425] dl-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane;

[0426] Meso-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane;

[0427] 1,2-Dichloro-3,3,4,4,4-pentafluorobut-1-ene;

[0428] 2,3-Dichloro-1,1,1,3-Tetrafluoropropane;

[0429] 1,2-Dichloro-1,1,2,4,4,4-hexafluorobutane;

[0430] 1,2,2-Trichloro-1,1-Difluoroethane;

[0431] 1,1,1-Trichloro-2,2-difluoroethane;

[0432] 1,1,2,2-Tetrachloro-1,2-difluoroethane;

[0433] 1,1,1,2-Tetrachloro-2,2-difluoroethane;

[0434] 1,2,3-trichloro-1,1,4,4,4-pentafluorobutane; and

[0435] 1,1,2,3-Tetrachloro-4,4,4-trifluorobut-1-ene.

[0436] In some implementations, the seventh stream S16 contains more than about 95 mol% of Z-HCFO-1326mxz.

[0437] In some implementations, based on the total weight of the first fraction, the trace HF in the seventh stream S16 is about 500 ppm or less, about 250 ppm or less, or about 100 ppm or less.

[0438] In one embodiment, a sixth feed stream S15, comprising or consisting substantially of HF and HCBD (more particularly unreacted HCBD and unreacted HF), is returned or recycled from the third distillation column D12 to reactor R10 for further participation in the conversion of HCBD and HF. In one embodiment, reactor R10 may be equipped with a condenser C10 (e.g., a partial condenser) to enhance the removal of hydrogen chloride gas and HCFO-1326mxz, as illustrated in the following reaction scheme:

[0439]

[0440] In the above reaction scheme, R-337mbf, R-1327mz, and R-338mf are perfluorinated products of HCFO-1326mxz, and R-336maf is an HCl adduct of HCFO-1326mxz. Partial condenser C10 allows HCFO-1326mxz, HF, and HCl to escape from reactor R10, preventing the formation of these perfluorinated products.

[0441] like Figure 1 As shown, a preferred embodiment of a system for generating HCFO-1326mxz from HCBD includes a reactor R10 for producing a composition comprising, or substantially comprising, HCBD, and a series of distillation columns D10, D11, and D12 for separating, purifying, and recovering HCBD. The system may also include a condenser C10 (e.g., a partial condenser) to enhance the removal of hydrogen chloride gas and HCFO-1326mxz.

[0442] like Figure 1 As shown, a preferred embodiment of the present invention provides a method for purifying a mixture containing HCFO-1326mxz. The method includes providing the mixture to a series of distillation columns D10, D11, D12 for purifying and recovering compositions containing HCFO-1326mxz, or substantially composed of it, and recycling unreacted HCBD and HF from this series of distillation columns for reacting HCBD with HF to produce the mixture.

[0443] System B and Method 1, Implementation Scheme 2

[0444] Figure 2 A schematic diagram of a system and method for generating HCFO-1326mxz from HCBD according to one embodiment of the present invention is shown. Figure 2 As shown, a preferred embodiment of the system includes a reactor R20, a first distillation column D20 in flow communication with the reactor R20, a second distillation column D21 in flow communication with the first distillation column D20 and the reactor R20, and an acid neutralizer A20 in flow communication with the second distillation column D21.

[0445] refer to Figure 2 HCBD is introduced into reactor R20 via feed stream F20. Anhydrous hydrogen fluoride (HF) is introduced into reactor R20 via feed stream F21. In some embodiments, an oxidant may be fed into reactor R20 via feed stream F22. Those skilled in the art will understand that an oxidant is not required in all cases. In reactor R20, HCBD is fluorinated in the presence of a catalyst to produce a product mixture comprising E- and Z-HCFO-1326mxz. The reaction is as follows:

[0446]

[0447] In some embodiments, the fluorination process is carried out by simply flowing HF, HCBD, and optionally an oxidant into a catalyst bed in reactor R20 at a specified temperature. In some embodiments, the process is carried out by flowing HF, HCBD, optionally an oxidant, and a carrier gas into a catalyst bed in the reactor. Examples of carrier gases include inert gases such as nitrogen, argon, and helium.

[0448] The desired reaction results can be achieved by appropriately selecting operating conditions such as temperature, contact time, and the ratio of HF to HCBD.

[0449] The reaction temperature for the catalytic fluorination of HCBD is in the range of about 80°C to about 150°C, or about 80°C to about 140°C. In some embodiments, the process is carried out at a temperature of about 90°C to about 135°C. By maintaining the reaction temperature within these ranges, the formation of byproducts can be reduced, and catalyst deactivation can be suppressed. However, those skilled in the art will understand that the catalytic fluorination of HCBD is an exothermic reaction, and temperatures exceeding about 150°C may locally occur within the reactor R20 or within the catalyst.

[0450] The contact time (CT) between reactants and catalyst in reactor R20 is determined by the following equation:

[0451] ,

[0452] Where VR is the volume (m³) of reactor R20 in cubic meters. 3 ), and VF is the total liquid volumetric flow rate of the reactor feed (m). 3 / hr). In one embodiment, the contact time is in the range of about 0.1 to about 10 hours, including all values ​​and ranges therein. Those skilled in the art will understand that contact time can affect the selectivity and conversion rate of HCBD, and therefore the contact time can be adjusted as needed to a target time in the range of about 0.1 hours to about 10 hours, or to a target time shorter or longer than that range, to achieve the desired reaction results.

[0453] The reaction in reactor R20 is typically carried out at atmospheric pressure, or at a pressure below atmospheric pressure, or at a pressure above atmospheric pressure. That is, the reaction pressure in reactor R20 for the fluorination reaction is not critical and can be adjusted as needed to achieve the desired reaction results. In one embodiment, the catalytic fluorination reaction reactor R20 is carried out at a pressure above atmospheric pressure, for example, because the increased pressure would reduce the size of the equipment used for the reaction. In one embodiment, the pressure within reactor R20 is in the range of about 0 MPaG to 2.0 MPaG (gauge pressure).

[0454] The reaction mixture obtained in reactor R20 exits reactor R20 as a first feed stream S20 and is supplied to a first distillation column D20 to remove unreacted material and impurities. The reaction mixture (i.e., the first feed stream S20) comprises, substantially comprises, or consists of, unreacted HCBD (standard boiling point 213 °C), HCFO-1326mxz (standard boiling point 35 °C to 43 °C), unreacted HF (standard boiling point 20 °C), and HCl (standard boiling point -85 °C), wherein HCl is formed as a product of the fluorination reaction of HCBD and HF in reactor R20.

[0455] In some implementations, the first distillation column D20 operates at a pressure of about 300 psig or less, or about 200 psig or less.

[0456] The first distillation column D20 separates the first feed stream S20 into a first fraction containing HCl and impurities, substantially composed of or consisting of HCl, and a second fraction containing HCBD, HF, and HCFO-1326mxz, substantially composed of or consisting of HCBD, HF, and HCFO-1326mxz. The first fraction is removed from the first distillation column D20 in the second feed stream S21. In some embodiments, the composition of the second feed stream S21 in the second embodiment is the same as that of the second feed stream S11 in the first embodiment.

[0457] The second fraction is removed from the first distillation column D20 in the third feed stream S22. In some embodiments, the composition of the third feed stream S22 in this second embodiment is the same as that of the third feed stream S12 in the first embodiment.

[0458] A third feed stream S22 is then supplied from the first distillation column D20 to the second distillation column D21 to remove unreacted material and impurities. In some embodiments, the second distillation column D21 operates at a pressure of about 200 psig or lower, or about 150 psig or lower, or about 100 psig or lower. The second distillation column D21 separates the third feed stream S22 by distillation into a first fraction containing HCBD and HF, substantially composed of or consisting of them, and a second fraction containing an azeotrope of HF and HCFO-1326mxz, substantially composed of or consisting of them. The first fraction is removed from the second distillation column D21 in a fourth feed stream S23, and the second fraction is removed from the second distillation column D21 in a fifth feed stream S24.

[0459] A fourth feed stream S23, containing HCBD and HF, or consisting essentially of or composed of them, is returned or recycled from the second distillation column D21 to the reactor R20 for further conversion of HCBD and HF.

[0460] A fifth feed stream S24, comprising, substantially comprising, or consisting of an azeotrope of HF and HCFO-1326mxz, is supplied to acid neutralizer A20. A feed stream F23, comprising, substantially comprising, or consisting of water or a neutralizing agent such as potassium hydroxide, is co-fed with the fifth feed stream S24 to acid neutralizer A20. In some embodiments, acid neutralizer A20 operates at atmospheric pressure, or at a pressure of about 300 psig or less, or about 150 psig or less, or about 100 psig or less, or about 50 psig or less. Acid neutralizer A20 removes any acid present in the fifth feed stream S24, thereby separating the fifth feed stream S24 into a first fraction comprising, substantially comprising, or consisting of HCFO-1326mxz, and a second fraction comprising, substantially comprising, or consisting of neutralized HF. The first fraction leaves the acid neutralizer A20 as the sixth stream S25, and the second fraction leaves the acid neutralizer A20 as the seventh stream S26.

[0461] In some embodiments, the composition of the seventh stream S25 of the second embodiment is the same as that of the seventh stream S16 of the first embodiment, namely (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz), optional trace amounts of HF, and one or more additional compounds selected from those listed in Table 1. In some embodiments, the seventh stream S25 also contains about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less of water.

[0462] In one embodiment, reactor R20 may be equipped with a condenser (e.g., a partial condenser) to enhance the removal of hydrogen chloride gas and 1326 mg / z, as shown in the following reaction scheme:

[0463]

[0464] In the above reaction scheme, R-337mbf, R-1327mz, and R-338mf are perfluorinated products of HCFO-1326mxz, and R-336maf is an HCl adduct of HCFO-1326mxz. The condenser C20 allows HCFO-1326mxz, HF, and HCl to escape from reactor R20, preventing the formation of these perfluorinated products.

[0465] like Figure 2 As shown, a preferred embodiment of the system for producing HCFO-1326mxz from HCBD includes a reactor R20 for producing a composition comprising, consisting of, or substantially consisting of HCBD, a series of distillation columns D20, D21 for separating, purifying, and recovering HCBD, and an acid neutralizer A20 for further separating, purifying, and recovering HCBD. The system may also include a partial condenser to facilitate the escape of HCFO-1326mxz, HF, and HCl from reactor R20.

[0466] like Figure 2 As shown, a preferred embodiment of the present invention provides a method for purifying a mixture containing HCFO-1326mxz. The method includes providing the mixture to a series of distillation columns D20, D21 and an acid neutralizer for purifying and recovering compositions containing HCFO-1326mxz, or substantially composed therefrom, and recycling unreacted HCBD and HF from this series of distillation columns for reacting HCBD with HF to produce the mixture.

[0467] Additional details of Method 1

[0468] In any of the above-disclosed embodiments of Method 1, more than about 90 mol%, or more than about 95 mol%, more than about 97 mol%, more than about 99 mol%, more than about 99.5 mol%, or more than about 99.9 mol% of hexachlorobutadiene is converted to 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0469] In any of the above-disclosed embodiments of Method 1, the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced by the method provided herein is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene in greater than about 99 mol%, greater than about 99.5 mol%, or greater than about 99.7 mol%, or greater than about 99.9 mol%.

[0470] In any embodiment of the disclosed embodiments of Method 1 above, the composition produced by the system and method comprises:

[0471] i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); and

[0472] ii) Selected from one or more of the following additional compounds:

[0473] E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene,

[0474] E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0475] Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0476] HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene)

[0477] HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene),

[0478] HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene),

[0479] HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0480] HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0481] HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane)

[0482] HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane)

[0483] HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane)

[0484] HFC-356mff (1,1,1,4,4,4-hexafluorobutane)

[0485] HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane)

[0486] HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane)

[0487] HCFC-1122 (2-chloro-1,1-difluoroethylene)

[0488] HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane)

[0489] CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane)

[0490] CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane)

[0491] CFC-133a (2-chloro-1,1,1-trifluoroethane)

[0492] CFC-123 (2,2-dichloro-1,1,1-trifluoroethane)

[0493] CFC-123a (1,2-dichloro-1,1,2-trifluoroethane)

[0494] CFC-122 (1,2,2-trichloro-1,1-difluoroethane)

[0495] CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane),

[0496] HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane)

[0497] HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane)

[0498] HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane)

[0499] HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane)

[0500] HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and

[0501] E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

[0502] In some embodiments, the composition contains more than about 95 mol% of Z-HCFO-1326mxz.

[0503] In any of the above-disclosed embodiments of method 1, the method may be performed in batches or continuously.

[0504] In one implementation, after batch or continuous fluorination, HCFO-1326mxz has sufficient purity to require no further purification steps.

[0505] In another embodiment, HCFO-1326mxz can be recovered by any conventional method, including fractionation as described above, after the batch or continuous fluorination process is completed.

[0506] In any of the above-disclosed embodiments of Method 1, in a reaction of less than about 10 hours (e.g., less than about 8 hours, less than about 6 hours, less than about 5 hours), more than about 90 mol%, or more than about 95 mol%, or more than about 97 mol%, or more than about 99 mol%, or more than about 99.5 mol%, or more than about 99.9 mol% of hexachlorobutadiene is converted to 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0507] In any of the embodiments disclosed above in Method 1, the catalyst in reactors R10 and R20 is a fluorination catalyst. In some embodiments, the catalyst for fluorination of HCBD is a transition metal catalyst, and more preferably a Group V transition metal catalyst. In some embodiments, the Group V transition metal is niobium or tantalum. In some embodiments, the transition metal catalyst is selected from tantalum catalysts, niobium catalysts, or tantalum-niobium catalysts.

[0508] In some embodiments, the transition metal catalyst is a tantalum catalyst. In some embodiments, the transition metal catalyst is a tantalum halide catalyst. In some embodiments, the transition metal catalyst is tantalum chloride (V). In some embodiments, the transition metal catalyst is a niobium catalyst. In some embodiments, the transition metal catalyst is a niobium halide catalyst. In some embodiments, the transition metal catalyst is selected from niobium chloride (IV), niobium chloride (V), or mixtures thereof. In some embodiments, the transition metal catalyst is tantalum chloride (V), niobium chloride (IV), niobium chloride (V), or any mixture thereof.

[0509] In some embodiments, the transition metal catalyst is a mixture of tantalum and niobium catalysts. In some embodiments, the transition metal catalyst is a mixture of tantalum halide and niobium halide catalysts. In some embodiments, the transition metal catalyst is a mixture of tantalum chloride and niobium chloride.

[0510] In some embodiments, the transition metal catalyst is a mixture of tantalum chloride (V) and niobium chloride (IV). In some embodiments, the transition metal catalyst is a mixture of tantalum chloride (V) and niobium chloride (V). In some embodiments, the transition metal catalyst is a mixture of tantalum chloride (V), niobium chloride (IV), and niobium chloride (V).

[0511] In some embodiments, the catalyst for fluorination of HCBD is a Lewis acid catalyst, such as a metal halide catalyst, including but not limited to antimony halides, tin halides, thallium halides, iron halides, and combinations thereof. In some embodiments, metal chlorides and metal fluorides are employed, including but not limited to SbCl5, SbCl3, SbF5, SnCl4, TiCl4, NiF5, FeCl3, and combinations thereof.

[0512] In some embodiments, examples of liquid-phase fluorination catalysts include, but are not limited to, antimony halides, tin halides, tantalum halides, titanium halides, niobium halides, molybdenum halides, iron halides, fluorinated chromium halides, fluorinated chromium oxides, or combinations thereof. In some embodiments, examples of liquid-phase fluorination catalysts include, but are not limited to, SbCl5, SbCl3, SbF5, SnCl4, TaCl5, TiCl4, NbCl5, MoCl6, FeCl3, fluorinated forms of SbCl5, fluorinated forms of SbCl3, fluorinated forms of SnCl4, fluorinated forms of TaCl5, fluorinated forms of TiCl4, fluorinated forms of NbCl5, fluorinated forms of MoCl6, fluorinated forms of FeCl3, or combinations thereof. If these catalysts become deactivated, they can be readily regenerated by any means known in the art.

[0513] In one embodiment, the liquid-phase fluorination catalyst is selected from SbF5, SnCl4, TaCl5, TiCl4, NbCl5, and their fluorinated derivatives. In another embodiment, the liquid-phase fluorination catalyst is selected from SbF5, SnCl4, TaCl5, TiCl4, and / or their fluorinated derivatives. In yet another embodiment, the liquid-phase fluorination catalyst is SbF5 or SbCl5.

[0514] In some embodiments, the methods for preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene provided herein are carried out as liquid-phase methods. In some embodiments, the methods for preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (e.g., liquid-phase methods) are carried out in the absence of additional solvent components.

[0515] In some embodiments, the reaction zone temperature for the liquid-phase catalytic fluorination of HCBD is in the range of about 30°C to about 150°C, or about 50°C to about 150°C, about 50°C to about 140°C, about 70°C to about 140°C, or about 90°C to about 130°C. In some embodiments, the process is carried out at a temperature of about 80°C to about 150°C. By maintaining the reaction temperature within these ranges, the formation of byproducts can be reduced, and catalyst deactivation can be suppressed. However, those skilled in the art will understand that the catalytic fluorination of HCBD is an exothermic reaction, and temperatures exceeding the range of about 30°C to about 150°C may locally occur within the reactor or catalyst.

[0516] In some embodiments, the contact time (CT) between the reactants and the catalyst within the reactor ranges from about 0.1 to about 10 hours, including all values ​​and ranges therebetween. Those skilled in the art will understand that the contact time can affect the selectivity and conversion of HCBD, and therefore the contact time can be adjusted as needed to a target time in the range of about 0.1 hours to about 10 hours, or to a target time shorter or longer than this range, to achieve the desired reaction results.

[0517] In some embodiments, the reaction in the reactor is typically carried out at atmospheric pressure, or at a pressure below atmospheric pressure, or at a pressure above atmospheric pressure. That is, the reaction pressure in the reactor used for the fluorination reaction is not critical and can be adjusted as needed to achieve the desired reaction results. In one embodiment, the catalytic fluorination reaction in the reactor is carried out at a pressure above atmospheric pressure, for example, because the increased pressure would reduce the size of the equipment used for the reaction. In one embodiment, the pressure within the reactor is in the range of about 0 MPaG to 2.0 MPaG (gauge pressure).

[0518] In some embodiments, the catalytic fluorination method of this disclosure produces the desired product with high selectivity. In some embodiments of the invention, the product selectivity for compounds of the formula CF3CR=CClCF3, such as HCFO-1326mxz, is at least 90 mol% (Z to E ratio of 1:1), preferably at least 95 mol%, more preferably at least 99 mol%.

[0519] In some implementations, the method can be performed in batches or continuously.

[0520] In some implementations, an excess of HF is used based on 1 molar equivalent of hexachlorobutadiene, for example, an excess of HF of more than 1 molar equivalent, more than 2 molar equivalent, more than 5 molar equivalent, more than 10 molar equivalent, more than 20 molar equivalent, more than 50 molar equivalent, or more than 100 molar equivalent is used based on 1 molar equivalent of hexachlorobutadiene.

[0521] In some embodiments, based on 1 molar equivalent of hexachlorobutadiene, about 10 molar equivalents to about 50 molar equivalents of HF are used, for example, about 10 molar equivalents to about 40 molar equivalents, about 10 molar equivalents to about 30 molar equivalents, about 10 molar equivalents to about 20 molar equivalents, about 20 molar equivalents to about 50 molar equivalents, about 20 molar equivalents to about 40 molar equivalents, about 20 molar equivalents to about 30 molar equivalents, about 30 molar equivalents to about 50 molar equivalents, about 30 molar equivalents to about 40 molar equivalents, or about 40 molar equivalents to about 50 molar equivalents of HF. In some embodiments, based on 1 molar equivalent of hexachlorobutadiene, about 15 molar equivalents to about 20 molar equivalents of HF are used.

[0522] In some implementations, a catalytic amount of transition metal catalyst is used based on 1 molar equivalent of hexachlorobutadiene, for example, less than 0.85 molar equivalents, less than 0.6 molar equivalents, less than 0.4 molar equivalents, or less than 0.2 molar equivalents of transition metal catalyst based on 1 molar equivalent of hexachlorobutadiene.

[0523] In some embodiments, a metal halide catalyst of about 0.05 molar equivalents to about 0.5 molar equivalents is used based on 1 molar equivalent of hexachlorobutadiene. For example, a metal halide catalyst of about 0.05 molar equivalents to about 0.3 molar equivalents, about 0.05 molar equivalents to about 0.2 molar equivalents, about 0.05 molar equivalents to about 0.1 molar equivalents, about 0.1 molar equivalents to about 0.5 molar equivalents, about 0.1 molar equivalents to about 0.3 molar equivalents, or about 0.1 molar equivalents to about 0.2 molar equivalents, about 0.2 molar equivalents to about 0.5 molar equivalents, about 0.2 molar equivalents to about 0.3 molar equivalents, or about 0.3 molar equivalents to about 0.5 molar equivalents is used based on 1 molar equivalent of hexachlorobutadiene. In some embodiments, a metal halide catalyst of about 0.1 molar equivalents to about 0.3 molar equivalents is used based on 1 molar equivalent of hexachlorobutadiene.

[0524] In some embodiments, the method may include adding a fluorination catalyst to HF to form a first mixture, adding hexachlorobutadiene to the first mixture to form a second mixture, and then introducing the second mixture into a reactor for the fluorination of HCBD.

[0525] In one embodiment, the fluorination reaction is carried out in the absence of water. In some embodiments, if water is present, it is present in less than 1000 ppm by weight in one embodiment, or less than 500 ppm in another embodiment. In some embodiments, if water is present, it is present in less than about 50 ppm or less than about 25 ppm, or preferably less than about 15 ppm.

[0526] System C and Method 2

[0527] Figure 3 A schematic diagram of a system and method for producing hexafluoro-2-butyne (HFB) from 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) produced according to method 1 is shown, according to one embodiment of the present invention.

[0528] like Figure 3 As shown, a preferred embodiment of the system includes a reactor R30 for producing a reaction mixture containing HFB, a decanter E30 in flow communication with the reactor R30 and configured to receive the liquid portion of the reaction mixture formed in the reactor R30, a first distillation column D30 in flow communication with the decanter E30 and the reactor R30, and a second distillation column D31 in flow communication with the reactor R30 and configured to receive the vapor portion of the reaction mixture formed in the reactor R30.

[0529] refer to Figure 3 It will contain HCFO-1326mxz, and is substantially composed of or composed of HCFO-1326mxz. Figure 1 The seventh material flow S16 or Figure 2 The seventh feed stream S26 is fed into reactor R30 via feed stream F30. In reactor R30, HCFO-1326mxz undergoes dehydrochlorination to form HFB. More specifically, in reactor R30, HCFO-1326mxz reacts with a base containing an alkali metal hydroxide in the presence of a phase transfer catalyst to form hexafluorobutyne (HFB) (sometimes referred to herein as perfluorobutyryl-2-acetylene, PFBY). In addition to HFB, the product mixture from the dehydrochlorination of HCFO-1326mxz also contains water and byproduct salts, particularly alkali metal halide salts. The reaction is as follows:

[0530]

[0531] An alkali (e.g., a solution such as potassium hydroxide or sodium hydroxide) is fed into reactor R30 in feed stream F31.

[0532] In one embodiment, a phase transfer catalyst (PTC) is fed into reactor R30 in feed stream F32. In another embodiment, the dehydrochlorination process is carried out by flowing HCFO-1326mxz and an alkaline solution into a catalyst bed in reactor R30 at a specified temperature. In some embodiments, the process is carried out by flowing HCFO-1326mxz, an alkaline solution, and a carrier gas into a phase transfer catalyst bed in the reactor. Examples of carrier gases include inert gases such as nitrogen, argon, and helium.

[0533] In one embodiment, the phase transfer catalyst is an alkyl quaternary ammonium salt, wherein the alkyl group is an alkyl chain having four to twelve carbon atoms or four to ten carbon atoms. In one embodiment, the alkyl quaternary ammonium salt is a tetrabutylammonium salt. The anion of the salt can be a halide ion such as chloride or bromide ions, hydrogen sulfate ions, or any other commonly used anion.

[0534] In another embodiment, the alkyl quaternary ammonium salt is trioctylmethylammonium chloride (Aliquat 336). In another embodiment, the alkyl quaternary ammonium salt is tetraoctylammonium chloride. In yet another embodiment, the alkyl quaternary ammonium salt is tetraoctylammonium hydrogen sulfate.

[0535] Other compounds that are typically considered phase-transfer catalysts in other applications, including crown ethers, cavitation ligands, or nonionic surfactants alone, do not have a significant effect on the conversion or rate of the dehydrochlorination reaction in the same manner.

[0536] In another embodiment, HCFO-1326mxz(Z) can be dehydrochlorinated twice at temperatures well below 100°C using an alkaline aqueous solution in combination with an alkyl quaternary ammonium salt and additionally in combination with a nonionic surfactant, wherein the alkyl group is an alkyl chain having at least four or more carbon atoms. An example of such an alkyl quaternary ammonium salt is tetrabutylammonium chloride.

[0537] In yet another embodiment, the dehydrochlorination of HCFO-1326mxz(Z) can be achieved using an alkyl quaternary ammonium salt and in the presence of a nonionic surfactant, wherein the alkyl group is an alkyl chain having four to twelve carbon atoms. In one embodiment, the nonionic surfactant is ethoxylated nonylphenol or ethoxylated C12-C15 straight-chain fatty alcohol. Suitable nonionic surfactants include Bio-soft. ® N25-9 and Makon ® 10 are from Stepan Company.

[0538] In one embodiment, the alkyl quaternary ammonium salt is selected from: tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium hydrogen sulfate, trioctylmethylammonium chloride, trioctylmethylammonium bromide, tetradecylammonium chloride, tetradecylammonium bromide, and tetrachlorododecylammonium.

[0539] In one embodiment, the alkyl quaternary ammonium salt is a tetrabutylammonium salt. In another embodiment, the alkyl quaternary ammonium salt is a tetrahexylammonium salt. In yet another embodiment, the alkyl quaternary ammonium salt is a tetraoctylammonium salt. In still another embodiment, the alkyl quaternary ammonium salt is a trioctylmethylammonium salt.

[0540] The dehydrochlorination of HCFO-1326mxz(Z) can be achieved using an alkyl quaternary ammonium salt, wherein the alkyl group is an alkyl chain having at least one alkyl chain with eight or more carbons. In another embodiment, the alkyl quaternary ammonium salt has three alkyl chains having eight or more carbons, such as trioctylmethylammonium salt. In yet another embodiment, the alkyl quaternary ammonium salt is tetraoctylammonium salt. In yet another embodiment, the quaternary ammonium salt is tetra(dodecyl)ammonium salt. The anion of the salt can be a halide ion such as chloride or bromide ions, hydrogen sulfate ions, or any other commonly used anion.

[0541] In one embodiment, the alkyl quaternary ammonium salt is added in an amount of 0.5 mol% to 2.0 mol% of HCFO-1326mxz(Z). In another embodiment, the alkyl quaternary ammonium salt is added in an amount of 1 mol% to 2 mol% of HCFO-1326mxz(Z). In yet another embodiment, the alkyl quaternary ammonium salt is added in an amount of 1 mol% to 1.5 mol% of HCFO-1326mxz(Z). In one embodiment, the amount of alkyl quaternary ammonium salt added is 1 mol% to 1.5 mol% of HCFO-1326mxz(Z), and the weight of the added nonionic surfactant is 1.0 to 2.0 times the weight of the alkyl quaternary ammonium salt.

[0542] Exemplary bases include, but are not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, and mixtures thereof. Some exemplary strong bases include, but are not limited to, hydroxides, alkoxides, metal amides, metal hydrides, metal dialkylamides, and aromatic amines, wherein: alkoxides include lithium, sodium, and potassium salts of methyl, ethyl, and tert-butyl oxides; metal amides include sodium amide, potassium amide, and lithium amide; metal hydrides include sodium hydride, potassium hydride, and lithium hydride; and metal dialkylamides include lithium, sodium, and potassium salts of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, trimethylsilyl, and cyclohexyl-substituted amides.

[0543] In some embodiments, the base is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, and mixtures thereof.

[0544] In some embodiments, the base is an alkaline aqueous solution. As used herein, an "alkaline aqueous solution" is a liquid (e.g., a solution, dispersion, emulsion, or suspension) that is primarily an aqueous liquid having a pH greater than 7.

[0545] In some embodiments, the alkaline aqueous solution contains a small amount of an organic liquid that is miscible or immiscible with water. In some embodiments, the liquid medium in the alkaline aqueous solution is at least 90% water, for example, at least 95%, at least 97%, at least 98%, at least 99%, at least 99.5%, or at least 99.9%. In some embodiments, the water used in the alkaline aqueous solution is tap water. In some embodiments, the water used in the alkaline aqueous solution is deionized water or distilled water.

[0546] In a preferred embodiment, the base used for the dehydrochlorination reaction is an aqueous solution of sodium hydroxide, and the alkali metal halide salt produced as a byproduct is sodium chloride. The reaction is as follows:

[0547]

[0548] In some embodiments, based on one molar equivalent of HCFO-1326mxz, about 1 molar equivalent to about 5 molar equivalents of base are used, for example, about 1 molar equivalent to about 3 molar equivalents, about 1 molar equivalent to about 2 molar equivalents, about 1 molar equivalent to about 1.5 molar equivalents, about 1.5 molar equivalents to about 5 molar equivalents, about 1.5 molar equivalents to about 3 molar equivalents, about 1.5 molar equivalents to about 2 molar equivalents, about 2 molar equivalents to about 5 molar equivalents, about 2 molar equivalents to about 3 molar equivalents, or about 3 molar equivalents to about 5 molar equivalents of base. In some embodiments, based on one molar equivalent of HCFO-1326mxz, about 1 molar equivalent to about 1.5 molar equivalents of base are used. In some embodiments, based on one molar equivalent of HCFO-1326mxz, a molar excess of base is used.

[0549] In one implementation, the conversion rate of HCFO-1326mxz to HFB is at least 50% / hour.

[0550] The desired reaction results can be achieved by appropriately selecting operating conditions such as temperature, contact time, feed flow and / or catalyst ratio.

[0551] The reaction zone temperature for the dehydrochlorination of HCFO-1326mxz is in the range of about 0°C to about 150°C, or about 30°C to about 60°C, for example, about 30°C to about 50°C, about 30°C to about 40°C, about 40°C to about 60°C, about 40°C to about 50°C, or about 50°C to about 60°C. By maintaining the reaction temperature within these ranges, the formation of byproducts can be reduced, and catalyst deactivation can be suppressed.

[0552] The contact time (CT) between reactants and catalyst in the dehydrochlorination reactor R30 is determined by the following equation:

[0553] ,

[0554] Where VR is the volume (m³) of the dehydrochlorination reactor R30. 3 ), and VF is the total liquid volumetric flow rate of the reactor feed (m). 3 / hr). In one embodiment, the contact time is in the range of about 0.1 hours to about 20 hours, preferably about 0.5 hours to about 5 hours, including all values ​​and ranges therein. Those skilled in the art will understand that the contact time can affect the selectivity and conversion rate of HCFO-1326mxz to HFB, and therefore the contact time can be adjusted as needed to a target time in the range of about 0.1 hours to about 20 hours, or to a target time shorter or longer than this range, to achieve the desired reaction results.

[0555] The reactions in the dehydrochlorination reactor R30 are typically carried out at atmospheric pressure, or at pressures below atmospheric pressure, or at pressures above atmospheric pressure. That is, the reaction pressure in the dehydrochlorination reactor R30 for the dehydrochlorination reaction is not critical and can be adjusted as needed to achieve the desired reaction results. In one embodiment, the dehydrochlorination of the HCFO-1326mxz reaction in the dehydrochlorination reactor R30 is carried out at pressures ranging from approximately -0.05 MPaG to 1.8 MPaG (gauge pressure) to achieve improved reaction selectivity.

[0556] In some embodiments, the method for preparing HFB in the dehydrochlorination reactor R30 is carried out as a liquid-phase method. In some embodiments, the method for preparing HFB is carried out in the absence of additional solvent components.

[0557] The preparation of HFB can be carried out by batch or continuous methods.

[0558] In one implementation, after the batch or continuous dehydrochlorination process is completed, HFB has sufficient purity to require no further purification steps.

[0559] In another embodiment, HFB can be recovered by any conventional method, including fractionation, after the batch or continuous dechlorination process is completed.

[0560] The boiling point of the HCFO-1326mxz starting material is approximately 35°C, and the boiling point of HFB is approximately -25°C. Therefore, in one embodiment, the dehydrochlorination reactor R30 may be equipped with a condenser (e.g., a partial condenser) to enhance HFB removal and also prevent HFB decomposition upon contact with alkali, as shown in the following reaction scheme:

[0561] PFBY + 5NaOH --- 3NaF + CH3COONa + CF3COONa + H2O

[0562] In one embodiment, the reaction mixture obtained from the dehydrochlorination of HCFO-1326mxz in the dehydrochlorination reactor R30 comprises both a vapor portion and a liquid portion. A first feed stream S30 comprises the liquid portion of the reaction mixture and includes water, unreacted HCFO-1326mxz, excess PTC, and byproducts (such as salts formed in the reaction that form HFB, e.g., sodium chloride) that are substantially composed of or consist of these components. The first feed stream S30 consists of a separated aqueous phase and an organic liquid phase.

[0563] The first feed stream S30 is supplied from reactor R30 to decanter E30. In some embodiments, decanter E30 is operated at atmospheric pressure, or at a pressure of about 500 psig or less, or about 300 psig or less, or about 100 psig or less, or about 50 psig or less. The temperature of decanter E30 is not particularly limited and can be operated at decreasing, preferred, and increasing temperatures. In one embodiment, the operating temperature of decanter E30 is from about 0°C to about 50°C.

[0564] Decanter E30 separates the aqueous and organic liquid phases contained in feed stream S30 into a lower-density aqueous first fraction containing water and salts formed in the dehydrochlorination of HCFO-1326mxz, substantially composed of or consisting of the salts, and a higher-density organic second fraction containing HCFO-1326mxz, excess PTC, and other organic byproducts from the dehydrochlorination reaction, substantially composed of or consisting of the organic byproducts, and consisting of the organic byproducts, and consisting of the organic byproducts, respectively. The first fraction is removed from decanter E30 in second feed stream S31, and second feed stream S31 is removed from the process.

[0565] The second fraction is removed from the decanter E30 as the third stream S32. A first portion of the third stream S32 is returned to reactor R30 via a fourth stream S33 (optionally through one or more filters) to further participate in the reaction to produce HFB. The remaining (second) portion of the third stream S32 is supplied to the first distillation column D30 as the fifth stream S34. The split ratio of the first and second portions of the third stream S32 can vary between 0% (directly returned to reactor R30 in the fourth stream S33) and 100% (directly returned to reactor R30 in the fourth stream S33). The split ratio can be adjusted as needed to achieve the desired reaction results and control the concentrations of impurities and PTC in the reaction system.

[0566] In some embodiments, the first distillation column D30 operates at a pressure of about 300 psig or less, or about 150 psig or less, or about 75 psig or less. In one embodiment, the operating pressure of the first distillation column D30 is slightly lower than the operating pressure of the decanter E30 to allow flow from the decanter E30 to the first distillation column D30.

[0567] In the first distillation column D30, the fifth feed stream S34 is separated by distillation into a lower-boiling first fraction containing HCFO-1326mxz and optionally other organic byproducts from the dehydrochlorination reaction, substantially composed of or consisting of them, and a higher-boiling second fraction containing HCFO-1326mxz, excess PTC, and other organic byproducts from the dehydrochlorination reaction, substantially composed of or consisting of them. Most of the HCFO-1326mxz supplied to the first distillation column D30 is removed from the column in the lower-boiling first fraction. The first fraction is removed from the first distillation column D30 via a sixth feed stream S35, which is returned to the dehydrochlorination reactor R30 for further reaction to produce HFB. The second fraction is removed from the first distillation column D30 via a seventh feed stream S36, which is ultimately removed from the process.

[0568] In some embodiments, the sixth stream S35 (first fraction) comprises (i) HCFO-1326mxz, (ii) one or more of trifluoroacetone and hexafluoro-2-butyne, and (iii) one or more of the additional compounds listed in Table 1. In some embodiments, the composition of the sixth stream S35 comprises more than about 95 mol% Z-HCFO-1326mxz, or more than 96 mol% Z-HCFO-1326mxz, or more than 97 mol% Z-HCFO-1326mxz, or more than 98 mol% Z-HCFO-1326mxz, or more than 99 mol% Z-HCFO-1326mxz.

[0569] In some embodiments, the water content of the composition of the sixth feed stream S35 is about 10,000 ppm or less, or 5,000 ppm or less, or about 4,000 ppm or less, or about 3,000 ppm or less, or about 1,000 ppm or less. In some embodiments, the composition of the sixth feed stream S35 contains about 100 ppm or less of a base and about 500 ppm or less of a phase transfer catalyst.

[0570] Referring back to reactor R30, the eighth feed stream S37 comprises the vapor portion of the reaction mixture and includes HFB (standard boiling point -24°C), HCFO-1326 MXZ, water, and other organic byproducts from the dehydrochlorination reaction, substantially composed of or consisting of therefrom. The eighth feed stream S37 is supplied from the dehydrochlorination reactor R30 to the second distillation column D31. In some embodiments, the second distillation column D31 is operated at a pressure of about 300 psig or less, or about 150 psig or less, or about 75 psig or less. In one embodiment, the operating pressure of the second distillation column D31 is slightly lower than the operating pressure of reactor R30 to allow flow from reactor R30 to the second distillation column D31.

[0571] The second distillation column D31 separates the eighth feed stream S37 into a first fraction containing HFB, substantially composed of HFB, and a second fraction containing HCFO-1326mxz, water, and other organic byproducts from the dehydrochlorination reaction, substantially composed of HFB. The second fraction is removed from the second distillation column D31 via a ninth feed stream S38, which is primarily composed of HCFO-1326mxz. The ninth feed stream S38 is returned to reactor R30 for further reaction to produce HFB.

[0572] In some embodiments, the ninth stream S38 (second fraction) comprises (i) HCFO-1326mxz, (ii) one or more of trifluoroacetone, trifluoropropyne, and hexafluoro-2-butyne, and (iii) one or more of the additional compounds listed in Table 1. In some embodiments, the composition of the ninth stream S38 comprises greater than about 95 mol% Z-HCFO-1326mxz, or greater than 96 mol% Z-HCFO-1326mxz, or greater than 97 mol% Z-HCFO-1326mxz, or greater than 98 mol% Z-HCFO-1326mxz, or greater than 99 mol% Z-HCFO-1326mxz.

[0573] In some embodiments, the water content of the composition of the ninth flow S38 is about 5000 ppm or less, or about 4000 ppm or less, or about 3000 ppm or less, or about 1000 ppm or less.

[0574] Most of the HFB supplied to the second distillation column D31 is removed from the column in the lower boiling point fraction stream S39.

[0575] In one embodiment, the lower-boiling first fraction is removed from the second distillation column D31 via a tenth feed stream S39, which consists primarily of HFB and HCFO-1326mxz, water, and other organic byproducts from the dehydrochlorination reaction. The lower-boiling fraction (feed stream S39) from the second distillation column D31 can then be supplied to the third distillation column D32. The pressure of the third distillation column D32 is not particularly limited and can be operated at reduced, preferred, and increased pressures. In one embodiment, the operating pressure of the third distillation column D32 is from about 0.1 MPaG to about 0.5 MPaG.

[0576] In another embodiment, the lower boiling point first fraction is optionally removed from the second distillation column D31 via a tenth feed stream S39, which consists mainly of HFB. The desired product HFB can then be recovered from the tenth feed stream S39 and used, for example, to produce HCFO-1336mzz(Z).

[0577] The third distillation column D32 separates the components into lower-boiling and higher-boiling fractions. The lower-boiling fraction contains the desired product from this process step, HFB, and is removed from the third distillation column D32 in feed stream S3-10. The majority of the HFB supplied to the third distillation column D32 is removed from the column in the eleventh feed stream S3-10, which contains the lower-boiling fraction. The eleventh feed stream S3-10 is removed from the process. The higher-boiling fraction is removed from the third distillation column D32 in the twelfth feed stream S3-11. The twelfth feed stream S3-11 contains, consists of, or is substantially composed of: HCFO-1326mxz, water, and other organic byproducts from the dehydrochlorination reaction.

[0578] Optionally, the higher-boiling fraction from the third distillation column D32 can be supplied to the fourth distillation column D33 in the twelfth stream S3-11. The fourth distillation column D33 separates the components into lower-boiling and higher-boiling fractions. The lower-boiling fraction comprises, consists of, or is substantially composed of: HCFO-1326mxz; 1,1,1,4,4,4-hexafluoro-but-2-ene (HCFO-1336mzz); water; and other lower-boiling organic byproducts from the dehydrochlorination reaction. The lower-boiling fraction exits the fourth distillation column D33 in the thirteenth stream S3-12. The thirteenth stream S3-12 is removed from the process. The higher-boiling fraction is removed from the fourth distillation column D33 in the fourteenth stream S3-13. The fourteenth stream S3-13 comprises, consists of, or is substantially composed of: HCFO-1326mxz, water, and other organic byproducts from the dehydrochlorination reaction.

[0579] The fourteenth feed stream S3-13, containing HCFO-1326mxz, water, and other organic byproducts, is returned to reactor R30 for further participation in the dehydrochlorination reaction to produce HFB.

[0580] In one embodiment, the operating pressure of the fourth distillation column D33 is slightly lower than that of the third distillation column D32 to allow flow from the third distillation column D32 to the fourth distillation column D33.

[0581] like Figure 3 As shown, a preferred embodiment of a system for generating HFB from HCFO-1326mxz includes a reactor R30 for producing a composition containing, comprising, or substantially comprising HFB, a decanter for removing water and salt from the composition, and a series of distillation columns D30, D31, D32, and D33 for separating, purifying, and recovering HFB. The system may also include a partial condenser to facilitate the recovery of HFB products from reactor R30.

[0582] like Figure 3 As shown, a preferred embodiment of the present invention provides a method for purifying a mixture containing HFB. The method includes providing the mixture to a series of distillation columns D30, D31, D32, and D33 for purifying and recovering compositions containing, comprising, or substantially comprising HFB, and recycling unreacted HCFO-1326mxz from this series of distillation columns for dehydrochlorination to produce the HFB-containing mixture.

[0583] In one embodiment, the above-described HCFO-1326mxz dehydrochlorination system and method produce a composition comprising:

[0584] i) hexafluorobutyne; and

[0585] ii) Selected from one or more of the following additional compounds:

[0586] 1,1,1,3,3,3-Hexafluoropropane;

[0587] 1,1,1,2,4,4,4-Hepenofluoro-2-butene;

[0588] (E)-1,1,1,4,4,4-hexafluorobutene;

[0589] 1,1,1,2,2,4,4,4-octafluorobutane;

[0590] 1,1,1,4,4,4-Hexafluorobutane;

[0591] 1,2-Dichloro-1,1,2,2-Tetrafluoroethane;

[0592] 2-Chloro-1,1,1-trifluoroethane;

[0593] (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0594] 1-Chloro-3,3,4,4,4-pentafluorobut-1-yne;

[0595] 1-Chloro-3,3,4,4,4-pentafluorobut-2-yne;

[0596] (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene;

[0597] 1,2-Dichloro-3,3,4,4,4-pentafluorobut-1-ene;

[0598] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0599] 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane;

[0600] 2-Chloro-1,1,1,3,3-pentafluoropropane;

[0601] 1-Chloro-1,1,3,3,3-pentafluoropropane;

[0602] (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0603] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane;

[0604] 2,2-Dichloro-1,1,1-trifluoroethane;

[0605] 1,2-Dichloro-1,1,2-trifluoroethane;

[0606] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane;

[0607] (E)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0608] 1,1,2-Trichloro-1,2,2-trifluoroethane;

[0609] (Z)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0610] 1-Chloro-3,3,3-trifluoroprop-1-yne;

[0611] 1,2-Dichloro-3,3,3-trifluoroprop-1-ene;

[0612] (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene;

[0613] 1-Chloro-1,1,2,4,4,4-hexafluoro-2-butene;

[0614] 2-Chloro-1,3,3,3-Tetrafluoroprop-1-ene;

[0615] 1,1,3,3,3-pentafluoroprop-1-ene; and

[0616] 2-Chloro-1,1,3,3,3-pentafluoroprop-1-ene;

[0617] In some embodiments, the composition contains more than about 95 mol% HFB.

[0618] System D and Method 3

[0619] Figure 4 A schematic diagram of a system and method for producing (Z)-1,1,1,4,4,4-hexafluoro-2-butene ((Z)-HFO-1336mzz) from HFB produced according to method 2 is shown, according to one embodiment of the present invention. Figure 4 As shown, a preferred embodiment of the system includes a reactor R40, a first distillation column D40 in flow communication with the reactor R40, and a second distillation column D41 in flow communication with the first distillation column D40. In one embodiment, the reactor R40 is a continuous gas-phase reactor containing a solid catalyst. In one embodiment, the reactor configuration for preparing Z-HFO-1336mzz can be a single reactor or multiple reactors connected in series.

[0620] refer to Figure 4 An eleventh feed stream S3-10, containing HFB, substantially composed of, or composed of HFB, is fed into reactor R40 via a first feed stream F40. In reactor R40, HFB undergoes hydrogenation in the presence of a catalyst to form HFO-1336mzz(Z) (standard boiling point 33°C). More specifically, in hydrogenation reactor R40, hydrogen gas is fed into reactor R40 together with the HFB-containing feed stream F40 via a second feed stream F41.

[0621] The hydrogenation reaction is shown below:

[0622]

[0623] In some embodiments, the hydrogenation process is simply carried out by flowing HFB and hydrogen into a catalyst bed in reactor R40 at a specified temperature. In some embodiments, the process is carried out by flowing HFB, hydrogen, and a carrier gas into a catalyst bed in reactor R40. Examples of carrier gases include inert gases such as nitrogen, argon, and helium.

[0624] By appropriately selecting operating conditions such as temperature, contact time, and the ratio of HFB to hydrogen, the desired reaction results can be achieved.

[0625] The reaction zone temperature for HFB hydrogenation is in the range of about 20°C to about 200°C, or about room temperature, about 40°C to about 90°C, about 60°C to about 90°C, or about 60°C to about 150°C. In some embodiments, the process is carried out at a temperature of about 60°C to about 120°C. By maintaining the reaction temperature within these ranges, the formation of byproducts can be reduced, and catalyst deactivation can be suppressed. However, those skilled in the art will understand that HFB hydrogenation is an exothermic reaction, and temperatures exceeding the range of about 30°C to about 200°C may locally occur within the hydrogenation reactor R40 or within the catalyst. The reactor pressure is 1 psig to 300 psig, 20 psig to 200 psig, or 40 psig to 100 psig.

[0626] In one embodiment, a thermal diluent can be used to reduce any temperature rise caused by the exothermic reaction. For example, the thermal diluent can be an inert material compatible with the method and injected into reactor R40.

[0627] In some embodiments, the method for preparing HFO-1336mzzZ is carried out as a liquid-phase method. In some embodiments, the method for preparing HFO-1336mzz is carried out in the absence of additional solvent components. In one embodiment, a controlled hydrogen feed is introduced into reactor R40 as a thermal diluent or a mitigating component.

[0628] In another embodiment, hydrogen is used as the hydrogen gas and the method for preparing HFO-1336mzzZ is carried out as a gas-phase method. In one embodiment, due to the exothermic nature of the reaction used to prepare HFO-1336mzzZ, in order to enhance thermal mitigation, multiple gas-phase reactors, such as multiple reactors R40, are arranged to carry out the hydrogenation reaction to prepare HFO-1336mzzZ.

[0629] The contact time (CT) between reactants and catalyst in hydrogenation reactor R40 is determined by the following equation:

[0630] ,

[0631] Where VR is the volume (m³) of the hydrogenation reactor R40. 3 ), and VF is the total liquid volumetric flow rate of the reactor feed (m). 3 / hr). In one embodiment, the contact time is in the range of about 1 to about 120 seconds, or about 1 to about 60 seconds, or about 5 to about 120 seconds, inclusive of all values ​​and ranges therein. Those skilled in the art will understand that contact time can affect the selectivity and conversion rate of HFB, and therefore the contact time can be adjusted as needed to a target time in the range of about 1 second to about 60 seconds, or to a target time shorter or longer than this range, to achieve the desired reaction results.

[0632] The reaction in hydrogenation reactor R40 is typically carried out at atmospheric pressure, or at a pressure below atmospheric pressure, or at a pressure above atmospheric pressure. That is, the reaction pressure in hydrogenation reactor R40 for the hydrogenation reaction is not critical and can be adjusted as needed to achieve the desired reaction results. In one embodiment, the hydrogenation reaction in hydrogenation reactor R40 is carried out at a pressure above atmospheric pressure, for example, because the increased pressure would reduce the size of the equipment used for the reaction. In one embodiment, the pressure within hydrogenation reactor R40 is in the range of about 0 MPaG to 2.0 MPaG (gauge pressure).

[0633] Preferably, the method for preparing HFO-1336mzzZ is a gas-phase method.

[0634] The preparation of HFO-1336mzzZ can be carried out by batch or continuous methods.

[0635] In some embodiments, about 1 molar equivalent of hydrogen is used based on 1 molar equivalent of HFB. In some embodiments, hydrogenation based on 1 molar equivalent of HFB uses about 0.5 molar equivalents to about 1 molar equivalent of hydrogen. In some embodiments, hydrogenation based on 1 molar equivalent of HFB uses about 0.67 molar equivalents to about 1 molar equivalent of hydrogen.

[0636] In some embodiments, the hydrogenation catalyst is a palladium catalyst. In one embodiment, the catalyst is a palladium catalyst dispersed on alumina or titanium silicate, doped with silver and / or lanthanides, and having a low palladium loading. In one embodiment, the palladium loading is from 100 ppm to 5000 ppm. In another embodiment, the palladium loading is from 200 ppm to 5000 ppm. In one embodiment, the catalyst is doped with at least one of silver, cerium, or lanthanum. In one embodiment, the molar ratio of cerium or lanthanum to palladium is from 2:1 to 3:1. In one embodiment, the molar ratio of silver to palladium is about 0.5:1.0.

[0637] In some embodiments, the hydrogenation catalyst is a Lindelömer catalyst. As used herein, the term "Lindelömer catalyst" refers to a heterogeneous palladium catalyst supported on a calcium carbonate support, which has been deactivated or conditioned with a lead compound. The lead compound may be, for example, lead acetate, lead oxide, or any other suitable lead compound. In some embodiments, the Lindelömer catalyst is prepared by reducing a palladium salt in the presence of a calcium carbonate slurry and then adding a lead compound. In some embodiments, the palladium salt is palladium chloride. In some embodiments, the catalyst is deactivated or conditioned with quinoline. In some embodiments, the hydrogenation catalyst is a palladium catalyst dispersed on alumina or titanium silicate and doped with silver and / or lanthanides. In some embodiments, the palladium loading on alumina or titanium silicate is from 100 ppm to 5000 ppm. In some embodiments, the palladium loading on alumina or titanium silicate is from 200 ppm to 5000 ppm.

[0638] In some embodiments, the hydrogenation catalyst is doped with at least one of silver, cerium, or lanthanum. In some embodiments, the hydrogenation catalyst is doped with silver. In some embodiments, the molar ratio of silver to palladium is about 0.5:1.0. In some embodiments, the hydrogenation catalyst is doped with cerium or lanthanum. In some embodiments, the molar ratio of cerium or lanthanum to palladium is about 2:1 to about 3:1.

[0639] In some implementations, hydrogenation based on 1 molar equivalent of HFB uses a catalytic amount (i.e., less than 1 molar equivalent) of hydrogenation catalyst.

[0640] In one embodiment of the continuous process, the mixture of HFB and hydrogen further comprises an inert carrier gas. In one embodiment, the inert carrier gas is selected from the group consisting of nitrogen, helium, or argon. In one embodiment, the inert carrier gas constitutes about 10% to about 80% of the gas fed into the continuous process. In another embodiment, the inert carrier gas constitutes about 20% to about 50% of the gas fed into the continuous process.

[0641] In one embodiment of the continuous process, the amount of palladium on the support in the lindra catalyst is 5% by weight. In another embodiment, the amount of palladium on the support in the lindra catalyst is greater than 5% by weight. In yet another embodiment, the amount of palladium on the support may be from about 5% by weight to about 1% by weight.

[0642] In some embodiments, the hydrogenation catalyst is used at a weight percentage of about 0.5 wt% to about 4 wt% based on the hydrogenation of HFB. In some embodiments, the hydrogenation catalyst is used at a weight percentage of about 1 wt% to about 3 wt% based on the hydrogenation of HFB. In some embodiments, the hydrogenation catalyst is used at a weight percentage of about 1 wt% to about 2 wt% based on the hydrogenation of HFB.

[0643] In some embodiments, HFO-1336mzz with a content greater than about 95 mol%, for example, greater than about 97 mol%, greater than about 98 mol%, greater than about 99 mol%, greater than about 99.5 mol%, and greater than about 99.9 mol%, is classified as Z-HFO-1336mzz. In some embodiments, HFO-1336mzz with a content greater than about 99 mol% is classified as Z-HFO-1336mzz.

[0644] In one implementation, Z-HFO-1336mzz has sufficient purity after the batch or continuous hydrogenation process is completed without the need for further purification steps.

[0645] In another embodiment, Z-HFO-1336mzz can be recovered by any conventional method, including, for example, fractionation, after the batch or continuous hydrogenation process is completed.

[0646] The reaction mixture obtained in hydrogenation reactor R40 exits R40 as a first feed stream S40. The first feed stream S40 (i.e., the reaction mixture) contains, is substantially composed of, or consists of unreacted HFB and HFO-1336mzz(Z). If used for hydrogenation, a thermal diluent may also be present in the first feed stream S40. Examples of thermal diluents include, but are not limited to, HFC-32, HFC-143a, HFC-134a, and HFC-134.

[0647] A first feed stream S40 is supplied from the hydrogenation reactor R40 to the first distillation column D40. In some embodiments, the first distillation column D40 operates at a pressure of about 300 psig or less, or about 200 psig or less, or about 100 psig or less. In one embodiment, the operating pressure of the first distillation column D40 is slightly higher than the operating pressure of the hydrogenation reactor R40 to allow flow from the first distillation column D40 to the reactor R40.

[0648] The first distillation column D40 separates the first feed stream S40 into a lower-boiling first fraction containing unreacted HFB, other lower-boiling organic byproducts from the hydrogenation reaction, and a thermal diluent (if used), which is substantially composed of or constitutes thereof, and a higher-boiling second fraction containing Z-HFO-1336mzz and other higher-boiling organic byproducts from the hydrogenation reaction, which is substantially composed of or constitutes thereof. The majority of the HFB supplied to the first distillation column D40 leaves the column in the lower-boiling first fraction. The first fraction is removed from the first distillation column D40 in the second feed stream S41. Preferably, the second feed stream S41 is returned to the hydrogenation reactor R40 for further participation in the reaction to produce HFB. The second fraction is removed from the first distillation column D40 in the third feed stream S42.

[0649] A third feed stream S42, comprising, substantially comprising, or consisting of Z-HFO-1336mzz and other higher-boiling organic byproducts from the hydrogenation reaction, is supplied from the first distillation column D40 to the second distillation column D41. In some embodiments, the second distillation column D41 is operated at a pressure of about 150 psig or less, or about 100 psig or less, or about 50 psig or less. In one embodiment, the operating pressure of the second distillation column D41 is slightly lower than that of the first distillation column D40 to allow flow from the first distillation column D40 to the second distillation column D41.

[0650] The second distillation column D41 separates the third feed stream S42 into a first lower-boiling fraction primarily composed of Z-HFO-1336mzz, 1,1,1,4,4,4-hexafluorobutane (HCFC-356mff), and other lower-boiling organic byproducts from the hydrogenation reaction, substantially composed of or consisting of them; and a second higher-boiling fraction primarily composed of Z-HFO-1336mzz and other higher-boiling organic byproducts from the hydrogenation reaction, substantially composed of or consisting of them. The first fraction is removed from the second distillation column D41 in a fourth feed stream S43. The second fraction, primarily composed of (Z)-HFO-1336mzz and other higher-boiling organic byproducts from the hydrogenation reaction, is removed from the second distillation column D41 in a fifth feed stream S44. A significant portion of the (Z)-HFO-1336mzz supplied to the second distillation column D41 is removed from the column in the higher-boiling fraction feed stream S44.

[0651] In one embodiment, the high-boiling fraction of the second distillation column D41 in the feed stream S44 may optionally be supplied to the third distillation column D42. In one embodiment, the operating pressure of the third distillation column D42 is slightly lower than that of the second distillation column D41 to allow flow from the third distillation column D41 to the second distillation column D40.

[0652] The third distillation column D42 separates the components of the fifth feed stream S44 into a lower-boiling first fraction containing Z-HFO-1336mzz, or substantially composed of Z-HFO-1336mzz, and a higher-boiling second fraction containing Z-HFO-1336mzz and higher-boiling organic byproducts from the hydrogenation reaction, or substantially composed of Z-HFO-1336mzz. The lower-boiling fraction, the desired product from this process step, Z-HFO-1336mzz, is removed from the process in the sixth feed stream S45. A significant portion of the Z-HFO-1336mzz supplied to the third distillation column D42 is removed from the column in the lower-boiling fraction feed stream S45. The higher-boiling fraction is removed from the third distillation column D42 in the seventh feed stream S46.

[0653] like Figure 4 As shown, a preferred embodiment of the system for producing Z-HFO-1336mzz from HFB includes a reactor R40 for producing a composition comprising or substantially comprising Z-HFO-1336mzz, and a series of distillation columns D40, D41, D42 for separating, purifying and recovering Z-HFO-1336mzz.

[0654] like Figure 4 As shown, a preferred embodiment of the present invention provides a method for purifying a mixture containing Z-HFO-1336mzz. The method includes providing the mixture to a series of distillation columns D40, D41, D42 for purifying and recovering compositions containing Z-HFO-1336mzz, or substantially composed of Z-HFO-1336mzz, and recycling unreacted HFB from this series of distillation columns for hydrogenation to produce a mixture containing Z-HFO-1336mzz.

[0655] In one embodiment, the above-described system and method for HFB hydrogenation produces a composition comprising:

[0656] i)(Z)-1,1,1,4,4,4-hexafluoro-2-butene; and

[0657] ii) Selected from one or more of the following additional compounds:

[0658] 1,1,1,3,3,3-Hexafluoropropane;

[0659] (E)-1,1,1,4,4,4-hexafluorobutene;

[0660] 1,1,1,2,2,4,4,4-octafluorobutane;

[0661] 1,2-Dichloro-1,1,2,2-Tetrafluoroethane;

[0662] 3-Chloro-1,1,1-trifluoropropane;

[0663] 4-Chloro-1,1,1,2,2-pentafluorobutane;

[0664] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0665] 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane;

[0666] 2-Chloro-1,1,1,3,3-pentafluoropropane;

[0667] 1-Chloro-1,1,3,3,3-pentafluoropropane;

[0668] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane;

[0669] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane;

[0670] 1,2-Dichloro-3,3,3-trifluoroprop-1-ene;

[0671] 1-Chloro-3,3,3-trifluoropropene;

[0672] 1-Chloro-1,1,2,4,4,4-hexafluoro-2-butene;

[0673] 1-Chloro-1,1,4,4,4-pentafluorobutane;

[0674] 2-Chloro-1,1,1,3-Tetrafluoropropane; and

[0675] 1,1,1,3,3-Pentafluoropropane;

[0676] The composition contains more than about 99 mol% of Z-HFO-1336mzz.

[0677] Integration Systems and Methods

[0678] This application also provides a method for preparing Z-HFO-1336mzz, the method comprising: i) reacting HCBD with HF in the presence of a fluorination catalyst to form a first composition comprising, consisting of, or substantially consisting of HCFO-1326mxz (two isomers); ii) reacting HCFO-1326mxz with a base comprising an alkali metal hydroxide in the presence of a phase transfer catalyst to form a second composition comprising, consisting of, or substantially consisting of HFB; and iii) reacting HFB with hydrogen in the presence of a hydrogenation catalyst to form a third composition comprising, consisting of, or substantially consisting of Z-HFO-1336mzz. The catalysts, reagents, process parameters, conversion rates, etc., of this integrated method embodiment may be selected from any of the disclosures provided above regarding the respective method embodiments.

[0679] This application also provides a method for preparing Z-HFO-1336mzz, the method comprising: i) reacting HCBD with HF in the presence of a fluorination catalyst to form a first composition comprising, consisting of, or substantially consisting of HCFO-1326mxz (two isomers); ii) recovering HCFO-1326mxz; iii) reacting HCFO-1326mxz with a base comprising an alkali metal hydroxide in the presence of a phase transfer catalyst to form a second composition comprising, consisting of, or substantially consisting of HFB; iv) recovering HFB; v) reacting HFB with hydrogen in the presence of a hydrogenation catalyst to form a third composition comprising, consisting of, or substantially consisting of Z-HFO-1336mzz; and vi) recovering Z-HFO-1336mzz. The catalysts, reagents, process parameters, conversion rates, etc., of this integrated method embodiment may be selected from any of the disclosures provided above regarding the respective method embodiments.

[0680] This application also provides a method for preparing Z-HFO-1336mzz, the method comprising: i) reacting HCBD with HF in the presence of a fluorination catalyst to form a first composition comprising or substantially comprising HCFO-1326mxz (two isomers); ii) reacting HCFO-1326mxz with an alkaline aqueous solution containing sodium hydroxide in the presence of a phase transfer catalyst to form a second composition comprising or substantially comprising HFB; and iii) reacting HFB with hydrogen in the presence of a hydrogenation catalyst to form a third composition comprising or substantially comprising Z-HFO-1336mzz. The catalysts, reagents, process parameters, conversion rates, etc., of this integrated method embodiment can be selected from any of the disclosures provided above regarding the respective method embodiments. These reactions are as follows:

[0681]

[0682]

[0683]

[0684]

[0685] In some embodiments, the present invention provides a system (System A) for preparing HCFO-1326mxz, the system comprising:

[0686] i) A reactor configured to react HCBD with HF in the presence of a catalyst to form a composition comprising HCFO-1326mxz (two isomers), HCl, unreacted HCBD, unreacted HF and optional impurities.

[0687] ii) A first distillation column configured to receive the composition from the reactor and configured to separate the first composition into a first fraction F1 containing HCl and impurities. D10 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D10 ;

[0688] iii) A second distillation column configured to receive a second fraction F2 from the first distillation column, comprising unreacted HCBD, unreacted HF, and HCFO-1326 ms. D10 It is configured to separate the second fraction into a third fraction F3 containing an azeotrope of unreacted HF and HCFO-1326mxz. D11 And the fourth fraction F4, which contains unreacted HCBD, unreacted HF, and HCFO-1326mxz. D11 The second distillation column is configured to distill the third fraction F3. D11 Return to the reactor; and

[0689] iv) A third distillation column configured to receive a fourth fraction F4 from the second distillation column, comprising unreacted HCBD, unreacted HF, and HCFO-1326 MXZ. D11 And is configured to deliver the fourth fraction F4 D11 The fifth fraction, F5, was separated into unreacted HF and unreacted HCBD. D12 And the sixth fraction F6 containing HCFO-1326mxz D12 The third distillation column is configured to distill the fifth fraction, F5. D12 Return to the reactor.

[0690] In some embodiments, the present invention provides a method for preparing and purifying HCFO-1326mxz, the method comprising:

[0691] i) In the presence of a catalyst, HCBD is reacted with HF in a reactor to form a first composition comprising HCFO-1326mxz (two isomers), HCl, unreacted HCBD, unreacted HF and optional impurities.

[0692] ii) The first composition is fed to a first distillation column, and the first composition is separated into a first fraction F1 containing HCl and impurities. D10And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D10 ;

[0693] iii) The second fraction F2 from the first distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326 ms, is... D10 The fraction is fed to the second distillation column, and the second fraction is separated into a third fraction F3 containing an azeotrope of unreacted HF and HCFO-1326mxz. D11 And the fourth fraction F4, which contains unreacted HCBD, unreacted HF, and HCFO-1326mxz. D11 ;as well as

[0694] iv) The fourth fraction F4 from the second distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326mxz, is... D11 It is supplied to the third distillation column, and the fourth fraction F4 is distilled. D11 The fifth fraction, F5, was separated into unreacted HF and unreacted HCBD. D12 And the sixth fraction F6 containing HCFO-1326mxz D12 ,

[0695] Optionally, the third fraction F3 D11 The second distillation column is recycled to the reactor, and optionally, the fifth fraction F5 is distilled therefrom. D12 The recycle is returned to the reactor from the third distillation column.

[0696] In some embodiments, the present invention provides a system (System B) for preparing HCFO-1326mxz, the system comprising:

[0697] i) A reactor configured to react HCBD with HF in the presence of a catalyst to form a composition comprising HCFO-1326mxz (two isomers), HCl, unreacted HCBD, unreacted HF and optional impurities.

[0698] ii) A first distillation column configured to receive the composition from the reactor and configured to separate the first composition into a first fraction F1 containing HCl and impurities. D20 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D20 ;

[0699] iii) A second distillation column configured to receive a second fraction F2 from the first distillation column, comprising unreacted HCBD, unreacted HF, and HCFO-1326 ms.D20 And is configured to transfer the second fraction F2 D20 The third fraction, F3, was separated into unreacted HF and unreacted HCBD. D21 And the fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz. D21 The second distillation column is configured to distill the third fraction F3. D21 Return to the reactor; and

[0700] iv) An acid neutralizer configured to receive the fourth fraction F4, which comprises an azeotrope of HF and HCFO-1326mxz, from the second distillation column. D21 And is configured to deliver the fourth fraction F4 D21 Separated into the fifth fraction F5, which contains neutralized HF. A20 And the sixth fraction F6 containing HCFO-1326mxz A20 .

[0701] In some embodiments, the present invention provides a method for preparing and purifying HCFO-1326mxz, the method comprising:

[0702] i) In the presence of a catalyst, HCBD is reacted with HF in a reactor to form a composition comprising HCFO-1326mxz (two isomers), HCl, unreacted HCBD, unreacted HF and optional impurities.

[0703] ii) The composition is fed to a first distillation column, and the first composition is separated into a first fraction F1 containing HCl and impurities. D20 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D20 ;

[0704] iii) The second fraction F2 from the first distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326 ms, is... D20 The second distillation column is supplied with the second fraction F2. D20 The third fraction, F3, was separated into unreacted HF and unreacted HCBD. D21 And the fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz. D21 ;as well as

[0705] iv) The fourth fraction F4, containing the azeotrope of HF and HCFO-1326mxz from the second distillation column. D21 Provided to the acid neutralizer, and the fourth fraction F4 is distilled. D21 Separated into the fifth fraction F5, which contains neutralized HF. A20And the sixth fraction F6 containing HCFO-1326mxz A20 ,

[0706] The third fraction F3 may be selected as an option. D21 It returns to the reactor from the second distillation column.

[0707] In some embodiments, the present invention provides a system (system C) for preparing HFB, the system comprising:

[0708] i) A reactor configured to react HCFO-1326mxz with an alkali containing an alkali metal hydroxide in the presence of a phase transfer catalyst to form a composition comprising a vapor portion and a liquid portion, the vapor portion comprising HFB and unreacted HCFO-1326mxz, the liquid portion comprising water, unreacted HCFO-1326mxz, excess phase transfer catalyst and alkali metal halide salt, the liquid portion comprising an aqueous liquid phase and an organic liquid phase;

[0709] ii) A decanter configured to receive the liquid portion of the composition from the reactor and configured to separate the aqueous liquid phase into a first fraction F1 comprising water and an alkali metal halide salt. E30 The organic liquid phase was separated into a second fraction, F2, containing unreacted HCFO-1326mxz and excess phase transfer catalyst. E30 The decanter is configured to transfer the second fraction F2 E30 The first part is returned to the reactor;

[0710] iii) A first distillation column configured to receive a second fraction F2 from a decanter. E30 The second part, and configured to deliver the second fraction F2 E30 The second part separated into a third fraction, F3, containing unreacted HCFO-1326mxz. D30 And the fourth fraction F4, which contains unreacted HCFO-1326mxz, excess PTC, and optional impurities. D30 The first distillation column is configured to distill the third fraction F3. D30 Return to the reactor; and

[0711] iv) A second distillation column configured to receive a vapor portion of the composition from the reactor and configured to separate the vapor portion into a fifth fraction F5 containing HFB. D31 And the sixth fraction F6 containing unreacted HCFO-1326mxz D31 The second distillation column is configured to distill the sixth fraction, F6. D31 Return to the reactor.

[0712] In some embodiments, the present invention provides a method for preparing HFB, the method comprising:

[0713] i) In the presence of a phase transfer catalyst, HCFO-1326mxz is reacted with an alkali containing an alkali metal hydroxide in a reactor to form a composition comprising a vapor portion and a liquid portion, the vapor portion comprising HFB and unreacted HCFO-1326mxz, the liquid portion comprising water, unreacted HCFO-1326mxz, excess phase transfer catalyst and alkali metal halide salt, and the liquid portion comprising an aqueous liquid phase and an organic liquid phase;

[0714] ii) The liquid portion of the composition from the reactor is provided to a decanter configured to separate the aqueous liquid phase of the liquid portion into a first fraction F1 comprising water and an alkali metal halide salt. E30 The organic liquid phase of the liquid portion was separated into a second fraction, F2, containing unreacted HCFO-1326mxz and excess phase transfer catalyst. E30 The second fraction F2 is optionally included. E30 The first part returns from the decanter to the reactor;

[0715] iii) The second fraction F2 from the decanter E30 The second portion is supplied to the first distillation column, and the second fraction F2 is... E30 The second part separated into a third fraction, F3, containing unreacted HCFO-1326mxz. D30 And the fourth fraction F4, which contains unreacted HCFO-1326mxz, excess PTC, and optional impurities. D30 The third fraction F3 is optionally included. D30 The recirculation from the first distillation column back to the reactor; and

[0716] iv) The vapor fraction of the composition from the reactor is fed to a second distillation column, and the vapor fraction is separated into a fifth fraction F5 containing HFB. D31 And the sixth fraction F6 containing unreacted HCFO-1326mxz D31 The sixth fraction F6 is optionally included. D31 The recycle is returned to the reactor from the second distillation column.

[0717] In some embodiments, the present invention provides a method (system D) for preparing Z-HFO-1336mzz, comprising:

[0718] i) a reactor configured to react HFB with hydrogen in the presence of a hydrogenation catalyst to form a composition comprising HFO-1336mzz(Z) and unreacted HFB; and

[0719] ii) A first distillation column configured to receive the composition from the reactor and configured to separate the composition into a first fraction F1 containing unreacted HFB. D40 and the second fraction F2 containing HFO-1336mzz(Z) D40 The first distillation column is configured to distill F1 D40 Return to the reactor.

[0720] In one embodiment of the system used to prepare Z-HFO-1336mzz, the second fraction F2 of the composition, in addition to HFO-1336mzz(Z), is... D40 It may also contain some impurities. The system also includes a second distillation column configured to receive the second fraction F2 from the first distillation column. D40 And it is configured to transfer the second fraction F2 D40 The third fraction, F3, was separated into HFO-1336mzz(Z), HFO-1336mzz(E), 1,1,4,4,4-hexafluorobutane (HCFC-356mff), and lower-boiling organic byproducts from the hydrogenation reaction. D41 And the fourth fraction F4, which contains HFO-1336mzz(Z) and higher-boiling organic byproducts from the hydrogenation reaction. D41 .

[0721] In some embodiments, the present invention provides a method for preparing and purifying Z-HFO-1336mzz, the method comprising:

[0722] iii) Reacting HFB with hydrogen in a reactor in the presence of a hydrogenation catalyst to form a composition comprising HFO-1336mzz(Z) and unreacted HFB; and

[0723] iv) The composition is fed from the reactor to a first distillation column, and the composition is separated into a first fraction F1 containing unreacted HFB. D40 and the second fraction F2 containing HFO-1336mzz(Z) D40 , where the first F1 can be chosen arbitrarily D40 It returns from the first distillation column to the reactor.

[0724] In one embodiment of the method for preparing and purifying Z-HFO-1336mzz, the second fraction F2 of the composition, in addition to HFO-1336mzz(Z), is... D40 It may also contain some impurities, and the method also includes the second fraction F2 from the first distillation column. D40 The second distillation column is supplied with the second fraction F2. D40The third fraction, F3, was separated into HFO-1336mzz(Z), HFO-1336mzz(E), 1,1,4,4,4-hexafluorobutane (HCFC-356mff), and lower-boiling organic byproducts from the hydrogenation reaction. D41 And the fourth fraction F4, which contains HFO-1336mzz(Z) and higher-boiling organic byproducts from the hydrogenation reaction. D41 .

[0725] In some implementations, the above systems and / or methods are integrated together to form a collective system and / or method for preparing HFO-1336mzz(Z) from HCBD.

[0726] Therefore, in one embodiment, the integrated system according to the invention includes a third distillation column D12 of system A and a second distillation column D31 of system C, the third distillation column being configured to distill a sixth fraction F6 containing HCFO-1326 mmol / L. D12 The dehydrochlorination reaction unit R30, supplied to system C, has a second distillation column configured to deliver the seventh fraction F7 containing HFB. D32 The hydrogenation reactor R40 is supplied to system D. In another embodiment, the integrated system according to the invention includes an acid neutralizer A20 of system B and a second distillation column D31 of system C, the acid neutralizer being configured to deliver a sixth fraction F6 containing HCFO-1326 mmol / L. A20 The dehydrochlorination reactor R30, supplied to system C, has a second distillation column configured to deliver the seventh fraction F7 containing HFB. D32 The hydrogenation reactor R40 is supplied to system D.

[0727] In another embodiment, the integrated purification method according to the present invention includes: purifying the sixth fraction F6 containing HCFO-1326 mg / z from the third distillation column D12 of system A. D12 The hydrogen chloride dechlorination reactor R30 of method 2 is supplied to produce HFB, and the seventh fraction F7 containing HFB from the second distillation column D31 of method 2 is supplied. D32 The hydrogenation reactor R40 of method 3 is provided to produce Z-HFO-1336mzz. In another embodiment, the integrated method according to the invention includes: taking the sixth fraction F6 containing HCFO-1326mxz from the acid neutralizer A20 of system B. A20 The dehydrochlorination reactor R30 of Method 2 is provided, as well as the seventh fraction F7 containing HFB from the second distillation column D31 of Method 2. D32 The hydrogenation reactor R40 is provided to method 3.

[0728] In some embodiments, the first composition comprises greater than about 95 mol%, greater than about 97 mol%, greater than about 98 mol%, greater than about 99 mol%, greater than about 99.5 mol%, or greater than about 99.9 mol% of Z-HCFO-1326mxz. In some embodiments, the first composition comprises greater than about 97 mol% of Z-HCFO-1326mxz.

[0729] In some embodiments, the second composition comprises more than about 95 mol%, more than about 97 mol%, more than about 98 mol%, more than about 99 mol%, more than about 99.5 mol%, or more than about 99.9 mol% of HFB.

[0730] In some embodiments, the third composition comprises more than about 95 mol%, more than about 97 mol%, more than about 98 mol%, more than about 99 mol%, more than about 99.5 mol%, or more than about 99.9 mol% of Z-HFO-1336mzz.

[0731] In some embodiments, the above-described integrated system and method produce a composition comprising:

[0732] i)(Z)-1,1,1,4,4,4-hexafluoro-2-butene; and

[0733] ii) Selected from one or more of the following additional compounds:

[0734] 1,1,1,3,3,3-Hexafluoropropane;

[0735] (E)-1,1,1,4,4,4-hexafluorobutene;

[0736] 1,1,1,2,2,4,4,4-octafluorobutane;

[0737] 1,2-Dichloro-1,1,2,2-Tetrafluoroethane;

[0738] 3-Chloro-1,1,1-trifluoropropane;

[0739] 4-Chloro-1,1,1,2,2-pentafluorobutane;

[0740] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0741] 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane;

[0742] 2-Chloro-1,1,1,3,3-pentafluoropropane;

[0743] 1-Chloro-1,1,3,3,3-pentafluoropropane;

[0744] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane;

[0745] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane;

[0746] 1,2-Dichloro-3,3,3-trifluoroprop-1-ene;

[0747] 1-Chloro-3,3,3-trifluoropropene;

[0748] 1-Chloro-1,1,2,4,4,4-hexafluoro-2-butene;

[0749] 1-Chloro-1,1,4,4,4-pentafluorobutane;

[0750] 2-Chloro-1,1,1,3-Tetrafluoropropane; and

[0751] 1,1,1,3,3-Pentafluoropropane;

[0752] The composition contains more than about 99 mol% of Z-HFO-1336mzz.

[0753] Composition

[0754] This application also provides compositions comprising a combination of a major component (e.g., Z-HCFO-1326mxz, HFB, or Z-HFO-1336mzz) and one or more additional compounds. In some embodiments, the compositions are prepared according to one or more of the methods described herein.

[0755] The additional compounds in the compositions described herein provide improved solubility of the active ingredients in the polymeric components of aerosols or foams. Furthermore, for refrigerant applications such as those used in air conditioning, heat pumps, refrigeration, and power cycles (e.g., organic Rankine cycles), the additional compounds can provide improved solubility with refrigerant lubricants (e.g., mineral oils, alkylbenzenes, synthetic paraffins, synthetic cycloalkanes, poly(α)olefins, polyol esters (POE), polyalkylene glycols (PAG), polyvinyl ethers (PVE), or perfluoropolyethers (PFPE) or mixtures thereof).

[0756] In addition, the presence of additional compounds in samples of Z-HCFO-1326mxz, HFB, or Z-HFO-1336mzz can be used to identify the method of manufacturing the compound.

[0757] Z-HCFO-1326mxz composition

[0758] This application also provides a composition comprising:

[0759] i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); and

[0760] ii) Selected from one or more of the following additional compounds:

[0761] E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene,

[0762] E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0763] Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene)

[0764] HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene)

[0765] HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene),

[0766] HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene),

[0767] HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0768] HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane)

[0769] HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane)

[0770] HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane)

[0771] HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane)

[0772] HFC-356mff (1,1,1,4,4,4-hexafluorobutane)

[0773] HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane)

[0774] HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane)

[0775] HCFC-1122 (2-chloro-1,1-difluoroethylene)

[0776] HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane)

[0777] CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane)

[0778] CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane)

[0779] CFC-133a (2-chloro-1,1,1-trifluoroethane)

[0780] CFC-123 (2,2-dichloro-1,1,1-trifluoroethane)

[0781] CFC-123a (1,2-dichloro-1,1,2-trifluoroethane)

[0782] CFC-122 (1,2,2-trichloro-1,1-difluoroethane)

[0783] CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane),

[0784] HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane)

[0785] HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane)

[0786] HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane)

[0787] HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane)

[0788] HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and

[0789] E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

[0790] In some embodiments, the composition contains more than about 95 mol% of Z-HCFO-1326mxz.

[0791] In some embodiments, the composition comprises one of Z-HCFO-1326mxz and an additional compound. In some embodiments, the composition comprises more than one of Z-HCFO-1326mxz and an additional compound (e.g., two or more; three or more; five or more; ten or more; etc.). In some embodiments, the composition comprises each of Z-HCFO-1326mxz and an additional compound. In some embodiments, the composition comprises one to twenty-five of Z-HCFO-1326mxz and an additional compound. In some embodiments, the composition comprises one to twenty of HCFO-1326mxz and an additional compound. In some embodiments, the composition comprises one to ten of HCFO-1326mxz and an additional compound. In some embodiments, the composition comprises one to five of HCFO-1326mxz and an additional compound. In some embodiments, the composition comprises one to four of HCFO-1326mxz and an additional compound. In some embodiments, the composition comprises one to three of HCFO-1326mxz and additional compounds. In some embodiments, the composition comprises one to two of HCFO-1326mxz and additional compounds.

[0792] In some embodiments, the composition comprises:

[0793] i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and

[0794] ii) Selected from one or more of the following additional compounds:

[0795] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0796] (E)-2-chloro-1,1,1,4,4,4-hexafluoro-butene;

[0797] 1,2-Dichloro-3,3,4,4-Tetrafluorocyclobut-1-ene;

[0798] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane; and

[0799] 1,1,2-Trichloro-1,2,2-trifluoroethane;

[0800] The composition contains more than about 95 mol% of (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

[0801] In some embodiments, the composition contains greater than about 97 mol% Z-HCFO-1326mxz. In some embodiments, the composition contains greater than about 98 mol% Z-HCFO-1326mxz. In some embodiments, the composition contains greater than about 99 mol% Z-HCFO-1326mxz. In some embodiments, the composition contains greater than about 99.5 mol% Z-HCFO-1326mxz. In some embodiments, the composition contains greater than about 99.9 mol% Z-HCFO-1326mxz.

[0802] In some embodiments, the composition consists essentially of Z-HCFO-1326mxz and one or more additional compounds.

[0803] Hexafluorobutyne (perfluorobut-2-yne) composition

[0804] This application also provides a composition comprising:

[0805] i) hexafluorobutyne; and

[0806] ii) Selected from one or more of the following additional compounds:

[0807] 1,1,1,3,3,3-Hexafluoropropane;

[0808] 1,1,1,2,4,4,4-Hepenofluoro-2-butene;

[0809] (E)-1,1,1,4,4,4-hexafluorobutene;

[0810] 1,1,1,2,2,4,4,4-octafluorobutane;

[0811] 1,1,1,4,4,4-Hexafluorobutane;

[0812] 1,2-Dichloro-1,1,2,2-Tetrafluoroethane;

[0813] 2-Chloro-1,1,1-trifluoroethane;

[0814] (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0815] 1-Chloro-3,3,4,4,4-pentafluorobut-1-yne;

[0816] 1-Chloro-3,3,4,4,4-pentafluorobut-2-yne;

[0817] (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene;

[0818] 1,2-Dichloro-3,3,4,4,4-pentafluorobut-1-ene;

[0819] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0820] 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane;

[0821] 2-Chloro-1,1,1,3,3-pentafluoropropane;

[0822] 1-Chloro-1,1,3,3,3-pentafluoropropane;

[0823] (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0824] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane;

[0825] 2,2-Dichloro-1,1,1-trifluoroethane;

[0826] 1,2-Dichloro-1,1,2-trifluoroethane;

[0827] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane;

[0828] (E)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0829] 1,1,2-Trichloro-1,2,2-trifluoroethane;

[0830] (Z)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0831] 1-Chloro-3,3,3-trifluoroprop-1-yne;

[0832] 1,2-Dichloro-3,3,3-trifluoroprop-1-ene;

[0833] (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene;

[0834] 1-Chloro-1,1,2,4,4,4-hexafluoro-2-butene;

[0835] 2-Chloro-1,3,3,3-Tetrafluoroprop-1-ene;

[0836] 1,1,3,3,3-pentafluoroprop-1-ene; and

[0837] 2-Chloro-1,1,3,3,3-pentafluoroprop-1-ene;

[0838] Trifluoroacetone;

[0839] Trifluoropropyne; and

[0840] 1,1,4,4,4-Pentafluoro-1-butene

[0841] The composition contains more than about 95 mol% HFB.

[0842] In some embodiments, the composition comprises one of HFB and an additional compound. In some embodiments, the composition comprises more than one of HFB and an additional compound (e.g., two or more; three or more; five or more; ten or more; etc.). In some embodiments, the composition comprises each of HFB and an additional compound. In some embodiments, the composition comprises one to twenty-five of HFB and an additional compound. In some embodiments, the composition comprises one to twenty of HFB and an additional compound. In some embodiments, the composition comprises one to ten of HFB and an additional compound. In some embodiments, the composition comprises one to five of HFB and an additional compound. In some embodiments, the composition comprises one to four of HFB and an additional compound. In some embodiments, the composition comprises one to three of HFB and an additional compound. In some embodiments, the composition comprises one to two of HFB and an additional compound.

[0843] In some embodiments, the composition comprises:

[0844] i) hexafluorobutyne; and

[0845] ii) Selected from one or more of the following additional compounds:

[0846] (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0847] (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and

[0848] Trifluoroacetone; Trifluoropropyne;

[0849] 1,1,4,4,4-Pentafluoro-1-butene,

[0850] The composition contains more than about 95 mol% HFB.

[0851] In some embodiments, the composition contains greater than about 97 mol% HFB. In some embodiments, the composition contains greater than about 98 mol% HFB. In some embodiments, the composition contains greater than about 99 mol% HFB. In some embodiments, the composition contains greater than about 99.5 mol% HFB. In some embodiments, the composition contains greater than about 99.9 mol% HFB.

[0852] In some embodiments, the composition consists essentially of HFB and one or more additional compounds.

[0853] (Z)-1,1,1,4,4,4-hexafluoro-2-butene composition

[0854] This application also provides a composition comprising:

[0855] i)(Z)-1,1,1,4,4,4-hexafluoro-2-butene; and

[0856] ii) Selected from one or more of the following additional compounds:

[0857] 1,1,1,3,3,3-Hexafluoropropane;

[0858] (E)-1,1,1,4,4,4-hexafluorobutene;

[0859] 1,1,1,2,2,4,4,4-octafluorobutane;

[0860] 1,2-Dichloro-1,1,2,2-Tetrafluoroethane;

[0861] 3-Chloro-1,1,1-trifluoropropane;

[0862] 4-Chloro-1,1,1,2,2-pentafluorobutane;

[0863] 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane;

[0864] 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane;

[0865] 2-Chloro-1,1,1,3,3-pentafluoropropane;

[0866] 1-Chloro-1,1,3,3,3-pentafluoropropane;

[0867] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane;

[0868] 1,2-Dichloro-1,1,3,3,3-pentafluoropropane;

[0869] 1,2-Dichloro-3,3,3-trifluoroprop-1-ene;

[0870] 1-Chloro-3,3,3-trifluoropropene;

[0871] 1-Chloro-1,1,2,4,4,4-hexafluoro-2-butene;

[0872] 1-Chloro-1,1,4,4,4-pentafluorobutane;

[0873] 2-Chloro-1,1,1,3-Tetrafluoropropane; and

[0874] 1,1,1,3,3-Pentafluoropropane;

[0875] (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and

[0876] (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene,

[0877] The composition contains more than about 99 mol% of Z-HFO-1336mzz.

[0878] In some embodiments, the composition comprises one of Z-HFO-1336mzz and an additional compound. In some embodiments, the composition comprises more than one of Z-HFO-1336mzz and an additional compound (e.g., two or more; three or more; five or more; ten or more; etc.). In some embodiments, the composition comprises each of Z-HFO-1336mzz and an additional compound. In some embodiments, the composition comprises one to ten of HFO-1336mzz and an additional compound. In some embodiments, the composition comprises one to five of HFO-1336mzz and an additional compound. In some embodiments, the composition comprises one to four of HFO-1336mzz and an additional compound. In some embodiments, the composition comprises one to three of HFO-1336mzz and an additional compound. In some embodiments, the composition comprises one to two of HFO-1336mzz and an additional compound.

[0879] In some embodiments, the composition comprises:

[0880] i)(Z)-1,1,1,4,4,4-hexafluoro-2-butene; and

[0881] ii) Selected from one or more of the following additional compounds:

[0882] (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

[0883] (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and

[0884] 2-Chloro-1,1,1,4,4,4-Hexafluorobutane,

[0885] The composition contains more than about 99 mol% of Z-HFO-1336mzz.

[0886] In some embodiments, the composition contains greater than about 97 mol% Z-HFO-1336mzz. In some embodiments, the composition contains greater than about 98 mol% Z-HFO-1336mzz. In some embodiments, the composition contains greater than about 99 mol% Z-HFO-1336mzz. In some embodiments, the composition contains greater than about 99.5 mol% Z-HFO-1336mzz. In some embodiments, the composition contains greater than about 99.9 mol% Z-HFO-1336mzz.

[0887] In some embodiments, the composition consists essentially of Z-HFO-1336mzz and one or more additional compounds.

[0888] How to use

[0889] The compositions provided herein (i.e., the compositions of the present invention) can be used in a wide range of applications, including their use as a refrigerant in high-temperature heat pumps, organic Rankine cycles, and as fire extinguishing / flame suppressants, propellants, foaming agents, solvents, and / or cleaning fluids.

[0890] In some embodiments, an additional compound of the composition containing at least one chlorine atom may provide improved solubility of the main component of the composition (e.g., (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, or hexafluorobutyne, or (Z)-1,1,1,4,4,4-hexafluoro-2-butene) in the aerosol or polymer component of the foam.

[0891] For example, unsaturated fluorocarbons, such as (Z)-1,1,1,4,4,4-hexafluoro-2-butene, exhibit different solubility than other fluorocarbon propellants. This reduced solubility may make it difficult to prepare single-phase, homogeneous aqueous aerosol formulations. The presence of low levels of chlorinated impurities can improve mixing and simplify the use of formulations and aerosol products.

[0892] Unsaturated fluorocarbons, such as (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, also exhibit different solubilities than other commonly used blowing agents. Reduced solubility can help promote pore growth during the foaming reaction, but these compounds may be difficult to mix. The presence of low levels of chlorinated impurities can improve mixing and foam processing properties without sacrificing the benefits of lower HFO solubility. Furthermore, chlorinated compounds typically have lower vapor thermal conductivity, thus imparting improved insulation properties to foam insulation products.

[0893] Furthermore, for refrigerant applications such as those used in air conditioning, heat pumps, refrigeration, and power cycles (e.g., organic Rankine cycles), additional compounds containing at least one chlorine atom can provide improved solubility with refrigerant lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic cycloalkanes, poly(α)olefins, polyol esters (POE), polyalkylene glycols (PAG), polyvinyl ethers (PVE), or perfluoropolyethers (PFPE) or mixtures thereof.

[0894] Furthermore, the additional compounds in the compositions presented herein can help improve leak detection capabilities. Refrigerant leaks can result in refrigerant loss from the system, thus increasing operating costs due to the need for refrigerant replenishment, and even the smallest loss of refrigerant from the system can affect normal operation. Finally, refrigerant leaks can lead to excessive environmental pollution. Specifically, even low levels of chlorinated compounds can increase the detectability of refrigerant at the leak point. Therefore, the system can be repaired or redesigned to prevent refrigerant leaks.

[0895] However, the content of additional compounds (e.g., additional chlorinated compounds) must be kept low, as higher levels can cause compatibility issues with structural materials. In aerosols, these compatibility issues may relate to the aerosol container (e.g., canister) or plastic valve components. In foams, these compatibility issues may involve equipment seals and gaskets. Furthermore, in aerosol products, the interactions of higher levels of additional compounds (e.g., chlorinated compounds) can lead to formulation instability. For example, in foam products, higher levels of chlorinated compounds can soften the foam, resulting in dimensional instability and poor strength.

[0896] The compositions described herein can also be used as low global warming potential (GWP) heat transfer compositions, refrigerants, power cycle working fluids, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, carrier fluids, displacement desiccants, polishing abrasives, polymerization media, expansion agents for polyolefins and polyurethanes, gaseous dielectrics, fire extinguishing agents, and flame retardants in liquid or gaseous form. In one embodiment, the compositions provided herein can be used as working fluids for transporting heat from a heat source to a radiator. Such heat transfer compositions can also be used as refrigerants in cycles, wherein the fluid undergoes a phase change (e.g., from liquid to gas and back to liquid, or vice versa, from gas to liquid and back to gas).

[0897] Examples of heat transfer systems include, but are not limited to, air conditioners, chillers, refrigeration units, heat pumps, water coolers, flooded evaporator coolers, direct expansion coolers, walk-in coolers, heat pumps, portable refrigeration units, portable air conditioning units, and combinations thereof.

[0898] In some embodiments, the compositions provided herein can be used in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or equipment. In some embodiments, the compositions can be used in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or equipment.

[0899] As used herein, a mobile heat transfer system refers to any refrigeration, air conditioning, or heating equipment integrated into a road, rail, sea, or air transport unit. Furthermore, mobile refrigeration, or air conditioning units include those devices independent of any mobile carrier and referred to as “integrated” systems. Such integrated systems include “containers” (sea / land combined transport) and “foldable containers” (road / rail combined transport).

[0900] As used herein, a stationary heat transfer system is a system that is fixed in one location during operation. Stationary heat transfer systems can be incorporated into or attached to any type of building, or can be freestanding installations located outside doors, such as soft drink vending machines. These stationary applications can be stationary air conditioning and heat pumps (including, but not limited to, coolers, high-temperature heat pumps, including transcritical heat pumps (e.g., where the condenser temperature is above 50°C, above 70°C, above 80°C, above 100°C, above 120°C, above 140°C, above 160°C, above 180°C, or above 200°C), residential, commercial, or industrial air conditioning systems, and include window coolers, tubeless coolers, ducted coolers, integral terminal coolers, and those located outside the building but connected to it, such as rooftop systems). In stationary refrigeration applications, the compositions provided herein can be used in high-temperature, medium-temperature, and / or low-temperature refrigeration equipment, including commercial, industrial, or residential refrigeration and freezing units, ice makers, independent coolers and freezers, flooded evaporator coolers, direct expansion coolers, walk-in and reach coolers and freezers, and combined systems. In some embodiments, the disclosed compositions can be used in supermarket refrigeration systems.

[0901] Therefore, according to the present invention, the compositions provided herein can be used in methods for generating cooling, generating heating, and transferring heat.

[0902] In some embodiments, this application provides a method for generating cooling, the method comprising evaporating the composition provided herein near the subject to be cooled, and then condensing the composition.

[0903] In some embodiments, this application provides a method for generating heat, the method comprising condensing the composition provided herein near a subject to be heated, and then evaporating the composition.

[0904] In some embodiments, this application provides a method of using the compositions provided herein as a heat transfer fluid composition. In some embodiments, the method includes transferring the composition from a heat source to a heat sink.

[0905] The compositions provided herein can also be used as low global warming potential (GWP) alternatives to currently used refrigerants, including but not limited to R-123 (i.e., HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R-11 (i.e., CFC-11, trichlorofluoromethane), R-245fa (i.e., HFC-245fa, 1,1,1,3,3-pentafluoropropane), R-114 (i.e., CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R-236fa (i.e., HFC-236a, 1,1,1,3,3,3-hexafluoropropane), R-236ea (i.e., HFC-236ea, 1,1,1,2,3,3-hexafluoropropane), and R-124 (i.e., HCFC-124, 2-chloro-1,1,1,2-tetrafluoroethane), etc.

[0906] In some embodiments, the compositions provided herein can be used as refrigerants and provide cooling performance (i.e., cooling capacity and energy efficiency) at least comparable to refrigerants for which alternatives are being sought. Furthermore, the compositions of the present invention can provide heating performance (i.e., heating capacity and energy efficiency) comparable to the refrigerants being replaced.

[0907] In some embodiments, this application provides a method for refilling a heat transfer system containing a refrigerant to be replaced and a lubricant, the method comprising removing the refrigerant to be replaced from the heat transfer system while retaining a majority of the lubricant in the system, and introducing one of the compositions of the present invention into the heat transfer system. In some embodiments, the lubricant in the system is partially replaced (e.g., replacing a portion of the mineral oil lubricant used with HCFO-123 with POE lubricant).

[0908] In some embodiments, the compositions of the present invention can be used to replenish refrigerant packing in a cooler. For example, if a cooler using HCFO-123 experiences performance degradation due to refrigerant leakage, the compositions provided herein can be added to restore performance to specifications.

[0909] This application also provides heat exchange systems comprising any of the compositions provided herein, wherein said systems are selected from air conditioners, refrigerators, chillers, heat pumps, water coolers, flooded evaporator coolers, direct expansion coolers, walk-in coolers, heat pumps, portable chillers, portable air conditioning units, and systems having combinations thereof. Furthermore, the compositions of the present invention can be used in secondary loop systems, wherein these compositions serve as the primary refrigerant, thus providing cooling for the secondary heat transfer fluid, thereby cooling remote locations.

[0910] Vapor compression refrigeration, air conditioning, or heat pump systems include an evaporator, compressor, condenser, and expansion unit. The vapor compression cycle reuses the refrigerant in multiple steps, producing a cooling effect in one step and a heating effect in different steps. The cycle can be simply described as follows: Liquid refrigerant enters the evaporator through the expansion unit, and by extracting heat from the environment, the liquid refrigerant boils at a low temperature in the evaporator to form vapor and produce cooling. The low-pressure vapor enters the compressor, where the vapor is compressed to increase its pressure and temperature. The high-pressure (compressed) vapor refrigerant then enters the condenser, where the refrigerant condenses and releases its heat to the environment. The refrigerant returns to the expansion unit, through which the liquid expands from the higher pressure level in the condenser to the lower pressure level in the evaporator, thus repeating the cycle.

[0911] This application also provides foam expanding agent compositions comprising the compositions of the present invention for preparing foam. In some embodiments, this application provides expandable compositions and methods for preparing foam, including but not limited to thermosetting (e.g., polyurethane, polyisocyanurate, or phenolic) foam compositions and thermoplastic (e.g., polystyrene, polyethylene, or polypropylene) foam compositions. In some embodiments, one or more of the compositions of the present invention may be included as foam expanding agents in the expandable composition, wherein the expandable composition may include one or more additional components capable of reacting and / or mixing and foaming under suitable conditions to form a foam or porous structure.

[0912] This application also provides a method for forming foam, the method comprising: (a) adding the composition of the present invention to a foamable composition; and (b) treating the foamable composition under conditions that effectively form foam.

[0913] This application also provides the use of the compositions of the invention as propellants in aerosol compositions. Additionally, this application provides aerosol compositions of the invention. The active ingredient to be aerosolized, along with inert components, solvents, and other materials, may also be present in the aerosol composition. In some embodiments, the aerosol composition is an aerosol. The compositions of the invention can also be used to formulate various industrial aerosols or other aerosol compositions, such as contact cleaners, dust collectors, lubricant sprays, release sprays, insecticides, etc., as well as consumer aerosols, such as personal care products (e.g., hairsprays, deodorants, and perfumes), household products (e.g., waxes, polishes, pot sprays, room fresheners, and household insecticides), and automotive products (e.g., cleaners and polishes), and pharmaceuticals such as anti-asthma and anti-halitosis medications. Examples include, but are not limited to, medications for treating asthma and other chronic obstructive pulmonary diseases and for delivering medications to accessible mucous membranes or via metered-dose inhalers (MDIs) for nasal administration.

[0914] This invention also provides a method for preparing aerosol products, the method comprising the step of adding the composition of the invention to a formulation of an aerosol container, wherein the composition of the invention serves as a propellant. Additionally, this application provides a method for producing aerosol products, the method comprising the step of adding the composition of the invention to a barrier-type aerosol packaging (e.g., a bag can or piston can), wherein the composition of the invention remains separate from other formulation components in the aerosol container, and wherein the composition of the invention serves as a propellant. Furthermore, this application provides a method for producing aerosol products, the method comprising the step of adding only the composition of the invention to an aerosol packaging, wherein the composition serves as an active ingredient (e.g., a dust collector, or a cooling or freezing spray).

[0915] This application also provides a method for converting heat from a heat source into mechanical energy, the method comprising heating a working fluid containing the composition of the present invention, and then expanding the heated working fluid. In this method, heating the working fluid uses heat supplied from a heat source; and as the pressure of the working fluid decreases, the expansion of the heated working fluid generates mechanical energy.

[0916] Methods for transferring heat can be subcritical, transcritical, or supercritical cycles. In a transcritical cycle, the working fluid is compressed to a pressure above its critical pressure before being heated, and then the working fluid pressure is reduced to below its critical pressure during expansion. In a supercritical cycle, the working fluid remains above its critical pressure throughout the cycle (e.g., compression, heating, expansion, and cooling).

[0917] Heat sources may include, for example, low-pressure steam, industrial waste heat, solar energy, geothermal hot water, low-pressure geothermal steam (primary or secondary arrangement), or distributed power generation equipment utilizing fuel cells or prime movers such as turbines, micro-turbines, or internal combustion engines. One type of low-pressure steam source can be a process known as a binary geothermal Rankine cycle. Large quantities of low-pressure steam are available in many places, such as in fossil fuel-powered power plants. Other heat sources include waste heat recovered from the exhaust gases of mobile internal combustion engines (e.g., truck or railway diesel engines or ships), waste heat from the exhaust gases of stationary internal combustion engines (e.g., stationary diesel generators), waste heat from fuel cells, heat obtained at combined heating, cooling and electrical or district heating and cooling equipment, waste heat from biomass fuel engines, waste heat from natural gas or methane gas burners or boilers that burn methane or methane fuel cells (e.g., distributed generation facilities) that operate with methane from a variety of sources including biogas, landfill gas and coalbed methane, heat from the combustion of bark and lignin at paper / pulp mills, heat from incinerators, heat from low-pressure steam from conventional steam power plants (to drive a “bottoming out” Rankine cycle), and geothermal energy.

[0918] In some embodiments, an organic Rankine power cycle is used for the heat conversion process. The heat obtained at relatively low temperatures, compared to steam (inorganic) power cycles, can be used to generate mechanical power using a Rankine cycle employing the working fluid described herein. In some embodiments, the working fluid is compressed before heating. Compression can be provided by a pump delivering the working fluid to a heat transfer unit (e.g., a heat exchanger or evaporator), where heat from a heat source is used to heat the working fluid. The heated working fluid then expands, reducing its pressure. Mechanical energy is generated during the expansion of the working fluid using an expander. Examples of expanders include, but are not limited to, turbine expanders or dynamic expanders (such as turbines), and positive displacement expanders (such as helical expanders, scroll expanders, and piston expanders). Examples of expanders also include vane expanders.

[0919] Mechanical power can be used directly (e.g., to drive a compressor) or converted into electrical power using an electric generator. In the power cycle of reusing the working fluid, the expanded working fluid is cooled. Cooling can be accomplished in a working fluid cooling unit (e.g., a heat exchanger or condenser). The cooled working fluid can then be used for repeated cycles (i.e., compression, heating, expansion, etc.). The same pump used for compression can be used to transfer the working fluid from the cooling stage.

[0920] This application also provides a method for detecting leaks from a container, the method comprising sampling the air near the container and detecting at least one additional compound of the composition provided herein using a leak detection device, wherein the container contains the composition of the invention. "Nearby" means within 12 inches of the outer surface of the container. Alternatively, "nearby" may be within 6 inches, 3 inches, or 1 inch of the outer surface of the container.

[0921] The container can be any known container, system, or device filled with the inventor's composition. Containers may include, but are not limited to, storage containers, transport containers, aerosol canisters, fire extinguishing systems, cooler devices, heat pump devices, heat transfer containers, and power cycle devices (e.g., organic Rankine cycle systems).

[0922] Devices for detecting leaks can be performed using any known sensor designed for leak detection. Specifically, devices for detecting leaks include, but are not limited to, electrochemical, corona discharge, and mass spectrometry leak detectors.

[0923] Several aspects and embodiments have been described above and are exemplary only, not limiting. After reading this specification, those skilled in the art will understand that other aspects and embodiments are possible without departing from the scope of the invention.

[0924] Example

[0925] The invention will be described in more detail through specific embodiments. The following embodiments are provided for illustrative purposes and are not intended to limit the invention in any way.

[0926] Example 1: System A and Method 1 for preparing high-purity Z-HCFO-1326mxz (Implementation Scheme 1)

[0927] NbCl5 (220 g) was added to a 5-gallon autoclave with a partial condenser, followed by HF activation at 100 °C. HF and hexachlorobutadiene (HCBD) were continuously co-fed into the autoclave. The total feed of HF was 700 g, and the total feed of HCBD was 600 g. HCFO-1326mxz was formed. The formed HCFO-1326mxz was continuously removed and based on... Figure 1 The system shown and as described above regarding Figure 1 Purified as described above. The final purity of (Z)-HCFO-1326mxz was greater than 98 mol%.

[0928] Example 2: System C and Method 2 for the preparation of high-purity hexafluoro-2-butyne

[0929] The following were prepared according to Example 1: KOH aqueous solution (1200 mL, 12 mol), Z-HCFO-1326mxz (purity >98%) (2000 g, 10 mol), and Aliquat. ® 336 (53 g, 0.1325 mol) and KCl (5% by weight aqueous solution) were co-fed into the dehydrochlorination reactor. The system and method used in this embodiment are similar to those used in other embodiments. Figure 3 The system shown is the same, and as mentioned above... Figure 3 The reaction temperature was controlled between 35°C and 40°C. This resulted in the formation of hexafluoro-2-butyne. Figure 3 The system shown and as described above regarding Figure 3 The resulting hexafluoro-2-butyne was purified as described above. The final purity of the hexafluoro-2-butyne was greater than 99.5 mol%.

[0930] Example 3: System D and Method 3 for preparing high-purity Z-HFO-1336mzz

[0931] 30 g of catalyst was packed into an 80-inch Hastelloy nickel alloy tubular reactor with an outer diameter of 1" OD (outer diameter) and a wall thickness of 0.074" . The catalyst was conditioned at 70°C with nitrogen (1000 sccm) and hydrogen (1000 sccm) streams at 200°C for one hour. The reactor was then cooled to 74°C. A mixture of hexafluoro-2-butyne (1090 sccm), hydrogen (218 sccm), and N2 (1090.6 sccm) produced according to Example 2 was then continuously fed into the reactor at a back pressure of 50 psig. Z-HFO-1336mzz was formed. Based on Figure 4 The system shown and as described above regarding Figure 4 The product was purified as described. The final purity of Z-HFO-1336mzz was greater than 99.5% by weight.

[0932] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. While methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety unless specific paragraphs are cited. In case of any conflict, this specification (including definitions) shall prevail. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting.

Claims

1. A system for purifying E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), said system comprising: A reactor configured to react hexachlorobutadiene (HCBD) with hydrofluoric acid (HF) in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD, and unreacted HF. A first distillation column is configured to receive the composition from the reactor and to separate the first composition into a first fraction F1 containing HCl. D10 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D10 ; A second distillation column is configured to receive, from the first distillation column, a second fraction F2 comprising unreacted HCBD, unreacted HF, and HCFO-1326mxz. D10 And configured to separate the second fraction into a third fraction F3 containing an azeotrope of unreacted HF and HCFO-1326mxz. D11 And the fourth fraction F4, which contains unreacted HCBD, unreacted HF, and HCFO-1326mxz. D11 The second distillation column is optionally configured to distill the third fraction F3. D11 Return to the reactor; as well as A third distillation column is configured to receive the fourth fraction F4, comprising unreacted HCBD, unreacted HF, and HCFO-1326mxz, from the second distillation column. D11 And is configured to deliver the fourth fraction F4 D11 The fifth fraction, F5, was separated into unreacted HF and unreacted HCBD. D12 And the sixth fraction F6 containing HCFO-1326mxz D12 The third distillation column is optionally configured to distill the fifth fraction F5. D12 Return to the reactor.

2. The system according to claim 1, wherein the first fraction F1 D10 Contains HCl, HF, and one or more additional compounds selected from the group consisting of: (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E-HCFO-1326mxz); (E)-(2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) (E-CFO-1317mx); (Z)- (2-Chloro-1,1,1,3,4,4,4-Hepanofluoro-2-butene) (Z-CFO-1317mx); 2-Chloro-1,1-difluoroethylene (HCFC-1122); 2-Chloro-1,1,1,2-tetrafluoroethane (HCFC-124); fluoropentachloroethane (CFC-111); 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114); 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113); 2-Chloro-1,1,1 - Trifluoroethane (CFC-133a); 2,2-Dichloro-1,1,1-trifluoroethane (CFC-123); 1,2-Dichloro-1,1,2-trifluoroethane (CFC-123a); 1,2,2-Trichloro-1,1-difluoroethane (CFC-122); 1,1,1,2-Tetrachloro-2,2-difluoroethane (CFC-112a); 1,1,1,3-Tetrafluoro-2,3,3-trichloropropane (HCFC-224db); 1,2-Dichloro-1,1,3-trifluoroethane 3,3-Pentafluoropropane (HCFC-225da); 2,3-Dichloro-1,1,1,3-Tetrafluoropropane (HCFC-234da); 2-Chloro-1,1,1,3,3-Pentafluoropropane (HCFC-235da); 1-Chloro-1,1,3,3,3-Pentafluoropropane (CFC-235fa); 1,1,1,3,3,3-Hexafluoropropane (HFC-236fa) and 1,1,1,2,4,4,4-Hepanofluoro-2-butene (HFO-1327mz).

3. The system of claim 2, wherein the first fraction F1 is used as the basis for... D10 The total weight of the HF is about 1% or less by weight, or about 0.5% or less by weight, or about 0.1% or less by weight.

4. The system of claim 2, wherein the first fraction F1 is used as the basis for... D10 The total weight present in the first fraction F1 D10 Each of the additional compounds is present in an amount of about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less.

5. The system of claim 2, wherein the first fraction F1 is used as the basis for... D10 The total weight of the first fraction F1 D10 The total amount of the additional compounds is about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less.

6. The system of claim 1, wherein the sixth fraction F6 D12 Include (iv)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); (v) Optional HF; and (vi) One or more additional compounds, said additional compounds being selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene) Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene) HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene) HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene), HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene), HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane) HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane) HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane) HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane) HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane) HFC-356mff (1,1,1,4,4,4-hexafluorobutane) HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane) HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane, HCFC-1122 (2-chloro-1,1-difluoroethylene) HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane) CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane) CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane) CFC-133a (2-chloro-1,1,1-trifluoroethane) CFC-123 (2,2-dichloro-1,1,1-trifluoroethane) CFC-123a (1,2-dichloro-1,1,2-trifluoroethane) CFC-122 (1,2,2-trichloro-1,1-difluoroethane) CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane), HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane, HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane) HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane) HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane) HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

7. The system of claim 1, wherein the sixth fraction F6 D12 Include (i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); (ii) Optional HF; and (iii) One or more additional compounds selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), E-Z-CFO-1317mx (E-2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) and Z-CFO-1317mx (Z-2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

8. The system according to any one of claims 6 and 7, wherein the sixth fraction F6 is used as the basis. D12 The total weight of the HF is about 1% or less by weight, or about 0.5% or less by weight, or about 0.1% or less by weight.

9. A system for purifying E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), said system comprising: A reactor configured to react hexachlorobutadiene (HCBD) with hydrofluoric acid (HF) in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD, and unreacted HF. A first distillation column is configured to receive the composition from the reactor and to separate the first composition into a first fraction F1 containing HCl. D20 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D20 ; A second distillation column is configured to receive, from the first distillation column, a second fraction F2 comprising unreacted HCBD, unreacted HF, and HCFO-1326mxz. D20 And configured to transfer the second fraction F2 D20 The third fraction, F3, was separated into unreacted HF and unreacted HCBD. D21 And the fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz. D21 The second distillation column is optionally configured to distill the third fraction F3. D21 Return to the reactor; as well as An acid neutralizer configured to receive the fourth fraction F4, comprising an azeotrope of HF and HCFO-1326mxz, from the second distillation column. D21 And is configured to deliver the fourth fraction F4 D21 Separated into the fifth fraction F5, which contains neutralized HF. A20 And the sixth fraction F6 containing HCFO-1326mxz A20 .

10. The system of claim 9, wherein the first fraction F1 D20 It comprises HCl, HF, and one or more additional compounds selected from the group consisting of: (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); (E)-2-chloro-1,1,1,4,4,34-hexafluoro-2-butene (E-HCFO-1326mxz); (E)-(2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) (E-CFO-1317mx); (Z) -(2-Chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) (Z-CFO-1317mx); 2-Chloro-1,1-difluoroethylene (HCFC-1122); 2-Chloro-1,1,1,2-tetrafluoroethane (HCFC-124); fluoropentachloroethane (CFC-111); 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114); 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113); 2-Chloro-1,1,1 - Trifluoroethane (CFC-133a); 2,2-Dichloro-1,1,1-trifluoroethane (CFC-123); 1,2-Dichloro-1,1,2-trifluoroethane (CFC-123a); 1,2,2-Trichloro-1,1-difluoroethane (CFC-122); 1,1,1,2-Tetrachloro-2,2-difluoroethane (CFC-112a); 1,1,1,3-Tetrafluoro-2,3,3-trichloropropane (HCFC-224db); 1,2-Dichloro-1,1,3-trifluoroethane 3,3-Pentafluoropropane (HCFC-225da); 2,3-Dichloro-1,1,1,3-Tetrafluoropropane (HCFC-234da); 2-Chloro-1,1,1,3,3-Pentafluoropropane (HCFC-235da); 1-Chloro-1,1,3,3,3-Pentafluoropropane (CFC-235fa); 1,1,1,3,3,3-Hexafluoropropane (HFC-236fa) and 1,1,1,2,4,4,4-Hepanofluoro-2-butene (HFO-1327mz).

11. The system of claim 10, wherein the first fraction F1 is used as the basis for... D20 The total weight of the HF is about 1% or less by weight, or about 0.5% or less by weight, or about 0.1% or less by weight.

12. The system of claim 10, wherein the first fraction F1 is used as the basis for... D20 The total weight present in the first fraction F1 D20 Each of the additional compounds is present in an amount of about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less.

13. The system of claim 10, wherein the first fraction F1 is used as the basis for... D20 The total weight of the first fraction F1 D20 The total amount of the additional compounds is about 1% by weight or less, or about 0.5% by weight or less, or about 0.1% by weight or less.

14. The system of claim 9, wherein the sixth fraction F6 A20 Include (iv)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); (v) Optional HF; and (vi) One or more additional compounds, said additional compounds being selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene) Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene) HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene) HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene), HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene), HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane) HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane) HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane) HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane) HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane) HFC-356mff (1,1,1,4,4,4-hexafluorobutane) HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane) HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane, HCFC-1122 (2-chloro-1,1-difluoroethylene) HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane) CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane) CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane) CFC-133a (2-chloro-1,1,1-trifluoroethane) CFC-123 (2,2-dichloro-1,1,1-trifluoroethane) CFC-123a (1,2-dichloro-1,1,2-trifluoroethane) CFC-122 (1,2,2-trichloro-1,1-difluoroethane) CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane), HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane, HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane) HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane) HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane) HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

15. The system of claim 9, wherein the sixth fraction F6 A20 Include (iv)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); (v) Optional HF; and (vi) One or more additional compounds selected from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), E-Z-CFO-1317mx (E-2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene) and Z-CFO-1317mx (Z-2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

16. The system of claim 15, wherein the sixth fraction F6 is used as the basis. A20 The total weight of the HF is about 1% or less by weight, or about 0.5% or less by weight, or about 0.1% or less by weight.

17. The system according to any one of claims 1 to 16, wherein the system further comprises a partial condenser coupled to the reactor.

18. A system for purifying hexafluoro-2-butyne (HFB), the system comprising: A reactor configured to react E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) with a base comprising an alkali metal hydroxide in the presence of a phase transfer catalyst to form a composition comprising a vapor portion and a liquid portion, the vapor portion comprising HFB and HCFO-1326mxz, the liquid portion comprising water, HCFO-1326mxz, excess phase transfer catalyst and alkali metal halide salt, the liquid portion consisting of an aqueous liquid phase and an organic liquid phase; A distillation column configured to receive the vapor portion of the composition from the reactor and configured to separate the vapor portion into a fraction F5 containing HFB. D31 And fraction F6 containing HCFO-1326mxz D31 The distillation column is configured to distill the fraction F6 containing HCFO-1326mxz. D31 Returning to the reactor, the distillation column is optionally configured to return the fraction F5 containing HFB. D31 Provided to one or more additional distillation columns.

19. The system of claim 18, wherein the system further comprises a partial condenser coupled to the reactor.

20. The system according to any one of claims 17 to 18, wherein the fraction F6 D31 Include: (iv)HCFO-1326mxz (v)(ii) One or more compounds selected from the group consisting of trifluoroacetone, trifluoropropyne, and hexafluoro-2-butyne, and (vi) Select one or more of the following additional compounds from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene) Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene) HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene) HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene), HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene), HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane) HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane) HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane) HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane) HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane) HFC-356mff (1,1,1,4,4,4-hexafluorobutane) HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane) HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane, HCFC-1122 (2-chloro-1,1-difluoroethylene) HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane) CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane) CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane) CFC-133a (2-chloro-1,1,1-trifluoroethane) CFC-123 (2,2-dichloro-1,1,1-trifluoroethane) CFC-123a (1,2-dichloro-1,1,2-trifluoroethane) CFC-122 (1,2,2-trichloro-1,1-difluoroethane) CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane), HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane, HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane) HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane) HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane) HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

21. The system according to any one of claims 18 to 20, wherein the fraction F6 D31 The water content is approximately 5000 ppm or less, or approximately 4000 ppm or less, or approximately 3000 ppm or less, or approximately 1000 ppm or less.

22. The system according to any one of claims 18 to 21, further comprising: A decanter, configured to receive the liquid portion of the composition from the reactor, and configured to separate the aqueous liquid phase into a first fraction F1 comprising water and the alkali metal halide salt. E30 The organic liquid phase was then separated into a second fraction, F2, containing unreacted HCFO-1326mxz and excess phase transfer catalyst. E30 The decanter is configured to decan the second fraction F2 E30 The first portion is returned to the reactor; as well as An additional distillation column, configured to receive the second fraction F2 from the decanter. E30 The second part, and configured to deliver the second fraction F2 E30 The second part was separated into a third fraction F3 containing unreacted HCFO-1326mxz. D30 And the fourth fraction F4, which contains unreacted HCFO-1326mxz and excess PTC. D30 The additional distillation column is configured to distill the third fraction F3 containing unreacted HCFO-1326mxz. D30 Return to the reactor.

23. The system of claim 22, wherein the third fraction F3 D30 include: (iv)HCFO-1326mxz (v)(ii) one or more of trifluoroacetone and hexafluoro-2-butyne, and (vi) Select one or more of the following additional compounds from the group consisting of: E-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, E-HFO-1316mxx (E-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene) Z-HFO-1316mxx (Z-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene) HFO-1327mz (1,1,1,2,4,4,4-heptafluoro-2-butene) HFO-1325lxz (1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene), HFO-1325dx (1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene), HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane) HFC-336maf (2,2-dichloro-1,1,1,4,4,4-hexafluorobutane) HFC-336lbf (1,2-dichloro-1,1,2,4,4,4-hexafluorobutane) HFC-337mbf (2-chloro-1,1,1,2,4,4,4-heptafluorobutane) HFC-337mde (2-chloro-1,1,1,3,4,4,4-heptafluorobutane) HFC-356mff (1,1,1,4,4,4-hexafluorobutane) HFC-346mdf (2-chloro-1,1,1,4,4,4-hexafluorobutane) HFC-338mf (1,1,1,2,2,4,4,4-octafluorobutane, HCFC-1122 (2-chloro-1,1-difluoroethylene) HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane) CFC-114 (1,2-dichloro-1,1,2,2-tetrafluoroethane) CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane) CFC-133a (2-chloro-1,1,1-trifluoroethane) CFC-123 (2,2-dichloro-1,1,1-trifluoroethane) CFC-123a (1,2-dichloro-1,1,2-trifluoroethane) CFC-122 (1,2,2-trichloro-1,1-difluoroethane) CFC-112a (1,1,1,2-tetrachloro-2,2-difluoroethane), HCFC-224db (1,1,1,3-tetrafluoro-2,3,3-trichloropropane, HFC-225da (1,2-dichloro-1,1,3,3,3-pentafluoropropane) HFC-235da (2-chloro-1,1,1,3,3-pentafluoropropane) HFC-235fa (1-chloro-1,1,3,3,3-pentafluoropropane) HFC-236fa (1,1,1,3,3,3-hexafluoropropane) and E- and Z-CFO-1317mx (2-chloro-1,1,1,3,4,4,4-heptafluoro-2-butene).

24. The system according to any one of claims 22 to 23, wherein the third fraction F3 D30 It contains approximately 100 ppm or less of the base.

25. The system according to any one of claims 22 to 24, wherein the third fraction F3 D30 It contains approximately 500 ppm or less of the phase transfer catalyst.

26. A system for purifying cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), said system comprising: A reactor configured to react hexafluoro-2-butyne (HFB) with hydrogen in the presence of a hydrogenation catalyst to form a composition comprising HFO-1336mzz(Z) and HFB. as well as A first distillation column is configured to receive the composition from the reactor and to separate the composition into a first fraction F1 containing HFB. D40 and the second fraction F2 containing HFO-1336mzz(Z) D40 The first distillation column is configured to distill the first fraction F1 D40 Return to the reactor.

27. The system of claim 26, wherein the reactor contains a thermal diluent, preferably selected from the group consisting of HFC-32, HFC-143a, HFC-134a and HFC-134.

28. The system according to any one of claims 26 to 27, further comprising a second distillation column configured to receive the second fraction F2 from the first distillation column. D40 And is configured to transfer the second fraction F2 D40 The third fraction, F3, was separated into HFO-1336mzz(Z), HFO-1336mzz(E), 1,1,4,4,4-hexafluorobutane (HCFC-356mff), and lower-boiling organic byproducts from the hydrogenation reaction. D41 And the fourth fraction F4, which contains HFO-1336mzz(Z) and higher-boiling organic byproducts from the hydrogenation reaction. D41 The system optionally further includes a third distillation column configured to receive the fourth fraction F4 from the second distillation column. D41 And is configured to deliver the fourth fraction F4 D41 Separated into a sixth fraction F6 containing Z-HFO-1336mzz D42 And the fifth fraction F5, which contains Z-HFO-1336mzz and higher-boiling organic byproducts from the hydrogenation reaction. D42 .

29. An integrated system for preparing Z-HFO-1336mzz from HCBD, the integrated system comprising the system according to claims 1 to 8, or the system according to claims 9 to 17, or the system according to claims 18 to 25, or the system according to claims 26 to 28.

30. The integrated system of claim 29, wherein the third distillation column of the system of claims 1 to 8 is configured to distill the sixth fraction F6 containing HCFO-1326mxz. D12 The system is supplied to the dehydrochlorination reactor of the system according to claims 18 to 25, and wherein the distillation column of the system according to claims 18 to 25 is configured to deliver the seventh fraction F7 containing HFB. D32 Supply to the hydrogenation reactor of the system according to claims 26 to 28.

31. The integrated system of claim 29, wherein the acid neutralizer A20 of the system of claims 9 to 17 is configured to contain the sixth fraction F6 comprising HCFO-1326mxz. A20 The system is supplied to the dehydrochlorination reactor of the system according to claims 18 to 25, and wherein the distillation column of the system according to claims 18 to 25 is configured to deliver the seventh fraction F7 containing HFB. D32 Supply to the hydrogenation reactor of the system according to claims 2 to 28.

32. A method for purifying E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), the method comprising: Hexachlorobutadiene (HCBD) is reacted with hydrofluoric acid (HF) in a reactor in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD and unreacted HF. The composition is fed to a first distillation column, and the composition is separated into a first fraction F1 containing HCl. D10 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D10 ; The second fraction F2 from the first distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326mxz, is... D10 The fraction is fed to a second distillation column, where it is separated into a third fraction, F3, containing an azeotrope of unreacted HF and HCFO-1326mxz. D11 And the fourth fraction F4, which contains unreacted HCBD, unreacted HF, and HCFO-1326mxz. D11 ; Optionally, the third fraction F3 D11 Return from the second distillation column to the reactor; The fourth fraction F4 from the second distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326mxz, is... D11 The fourth fraction F4 is supplied to the third distillation column. D11 The fifth fraction, F5, was separated into unreacted HF and unreacted HCBD. D12 And the sixth fraction F6 containing HCFO-1326mxz D12 ;as well as Optionally, the fifth fraction F5 D12 The product is returned from the third distillation column to the reactor.

33. A method for purifying E- and / or Z-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), the method comprising: Hexachlorobutadiene (HCBD) is reacted with hydrofluoric acid (HF) in a reactor in the presence of a fluorination catalyst to form a composition comprising HCFO-1326mxz, HCl, unreacted HCBD and unreacted HF. The composition from the reactor is provided to a first distillation column, and the first composition is separated into a first fraction F1 containing HCl. D20 And the second fraction F2 containing unreacted HCBD, unreacted HF and HCFO-1326mxz. D20 ; The second fraction F2 from the first distillation column, containing unreacted HCBD, unreacted HF, and HCFO-1326mxz, is... D20 The second fraction F2 is supplied to the second distillation column. D20 The third fraction, F3, was separated into unreacted HF and unreacted HCBD. D21 And the fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz. D21 ; Optionally, the third fraction F3 D21 Return from the second distillation column to the reactor; as well as The fourth fraction F4, which contains an azeotrope of HF and HCFO-1326mxz, from the second distillation column. D21 Provided to an acid neutralizer, the acid neutralizer being configured to neutralize the fourth fraction F4 D21 Separated into the fifth fraction F5, which contains neutralized HF. A20 And the sixth fraction F6 containing HCFO-1326mxz A20 .

34. A method for purifying hexafluoro-2-butyne (HFB), the method comprising: In the presence of a phase transfer catalyst, E- and / or Z-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz) is reacted with a base containing an alkali metal hydroxide in a reactor to form a composition comprising a vapor portion and a liquid portion, wherein the vapor portion comprises HFB and unreacted HCFO-1326mxz, and the liquid portion comprises water, unreacted HCFO-1326mxz, excess phase transfer catalyst, and an alkali metal halide salt, wherein the liquid portion consists of an aqueous liquid phase and an organic liquid phase; The vapor fraction of the composition from the reactor is provided to one or more distillation columns, and the vapor fraction is separated into a fraction F5 containing HFB. D31 And fraction F6 containing unreacted HCFO-1326mxz D31 ;as well as Optionally, the fraction F6 containing unreacted HCFO-1326mxz is included. D31 The product is returned from the distillation column to the reactor.

35. The method according to claim 34, further comprising: The liquid portion of the composition from the reactor is provided to a decanter, and the aqueous liquid phase is separated into a first fraction F1 containing water and the alkali metal halide salt. E30 The organic liquid phase is then separated into a second fraction, F2, containing the unreacted HCFO-1326mxz and an excess of phase transfer catalyst. E30 ; Optionally, the second fraction F2 E30 The first portion returns from the decanter to the reactor; The second fraction F2 from the decanter E30 The second portion is provided to an additional distillation column, and the second fraction F2 is... E30 The second part was separated into a third fraction F3 containing unreacted HCFO-1326mxz. D30 And the fourth fraction F4, which contains unreacted HCFO-1326mxz and excess PTC. D30 ;as well as Optionally, the third fraction F3 containing unreacted HCFO-1326mxz is included. D30 The distillation column returns the material to the reactor.

36. A method for purifying cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), the method comprising: In the presence of a hydrogenation catalyst, hexafluoro-2-butyne (HFB) is reacted with hydrogen in a reactor to form a composition comprising HFO-1336mzz(Z) and unreacted HFB. The composition from the reactor is provided to a first distillation column, and the composition is separated into a first fraction F1 containing unreacted HFB. D40 and the second fraction F2 containing HFO-1336mzz(Z) D40 ; as well as Optionally, the first fraction F1 D40 It returns from the first distillation column to the reactor.

37. The method of claim 36, further comprising taking the second fraction F2 from the first distillation column. D40 It is supplied to the second distillation column, and the second fraction F2 is... D40 The fraction was separated into a third fraction containing HFO-1336mzz(Z), HFO-1336mzz(E), 1,1,4,4,4-hexafluorobutane (HCFC-356mff) and lower-boiling organic byproducts from the hydrogenation reaction, and a fourth fraction F4 containing HFO-1336mzz(Z) and impurities. D41 .

38. An integrated method for purifying Z-HFO-1336mzz from HCBD, the integrated method comprising the method according to claims 32 and 34 to 37, wherein the integrated method comprises purifying the sixth fraction F6 containing HCFO-1326mxz from the third distillation column according to claim 32. D12 Provided to The dehydrochlorination reactor according to claim 34, and the seventh fraction F7 containing HFB from the distillation column according to claim 34. D32 Provided to The hydrogenation reactor according to claim 36.

39. An integrated method for purifying Z-HFO-1336mzz from HCBD, the integrated method comprising the method according to claims 33 to 37, the integrated method comprising purifying the sixth fraction F6 containing HCFO-1326mxz from the acid neutralizer A20 according to claim 33. A20 Provided to The dehydrochlorination reactor according to claim 34, and the seventh fraction F7 containing HFB from the distillation column according to claim 34. D32 Provided to The hydrogenation reactor according to claim 36.

40. A composition prepared by the system according to any one of claims 1 to 17 or the method according to any one of claims 32 to 33, the composition comprising: i)(Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and ii) Selected from one or more of the following additional compounds: 1,1,1,3,3,3-Hexafluoropropane; 1,1,1,2,2,4,4,4-octafluorobutane; 1,1,1,4,4,4-Hexafluorobutane; 1,2-Dichloro-1,1,2,2-Tetrafluoroethane; 2-Chloro-1,1,1-trifluoroethane; 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane; 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane; 2-Chloro-1,1,1,3,3-pentafluoropropane; 1-Chloro-1,1,3,3,3-pentafluoropropane; (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; 1,2-Dichloro-3,3,4,4-Tetrafluorocyclobut-1-ene; 2-Chloro-1,1,1,4,4,4-Hexafluorobutane; 2,2-Dichloro-1,1,1-trifluoroethane; 1,2-Dichloro-1,1,2-trifluoroethane; 1,2-Dichloro-1,1,3,3,3-pentafluoropropane; (E)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene; 1,1,2-Trichloro-1,2,2-trifluoroethane; (Z)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene; 1,2-Dichloro-3,3,3-trifluoroprop-1-ene; (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene; 2,2-Dichloro-1,1,1,4,4,4-hexafluorobutane; dl-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane; Meso-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane; 1,2-Dichloro-3,3,4,4,4-pentafluorobut-1-ene; 2,3-Dichloro-1,1,1,3-Tetrafluoropropane; 1,2-Dichloro-1,1,2,4,4,4-hexafluorobutane; 1,2,2-Trichloro-1,1-Difluoroethane; 1,1,1-Trichloro-2,2-difluoroethane; 1,1,2,2-Tetrachloro-1,2-difluoroethane; 1,1,1,2-Tetrachloro-2,2-difluoroethane; 1,2,3-trichloro-1,1,4,4,4-pentafluorobutane; and 1,1,2,3-Tetrachloro-4,4,4-trifluorobut-1-ene, The composition contains more than about 95 mol% of Z-HCFO-1326mxz.

41. A composition prepared by the system according to any one of claims 18 to 25 or the method according to any one of claims 34 to 35, the composition comprising: i) Hexafluorobutyne (HFB); and ii) One or more additional compounds, said additional compounds being selected from: 1,1,1,3,3,3-Hexafluoropropane; 1,1,1,2,4,4,4-Hepenofluoro-2-butene; (E)-1,1,1,4,4,4-hexafluorobutene; 1,1,1,2,2,4,4,4-octafluorobutane; 1,1,1,4,4,4-Hexafluorobutane; 1,2-Dichloro-1,1,2,2-Tetrafluoroethane; 2-Chloro-1,1,1-trifluoroethane; (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; 1-Chloro-3,3,4,4,4-pentafluorobut-1-yne; 1-Chloro-3,3,4,4,4-pentafluorobut-2-yne; (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene; 1,2-Dichloro-3,3,4,4,4-pentafluorobut-1-ene; 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane; 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane; 2-Chloro-1,1,1,3,3-pentafluoropropane; 1-Chloro-1,1,3,3,3-pentafluoropropane; (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; 2-Chloro-1,1,1,4,4,4-Hexafluorobutane; 2,2-Dichloro-1,1,1-trifluoroethane; 1,2-Dichloro-1,1,2-trifluoroethane; 1,2-Dichloro-1,1,3,3,3-pentafluoropropane; (E)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene; 1,1,2-Trichloro-1,2,2-trifluoroethane; (Z)-2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene; 1-Chloro-3,3,3-trifluoroprop-1-yne; 1,2-Dichloro-3,3,3-trifluoroprop-1-ene; (Z)-1,2-dichloro-1,1,4,4,4-pentafluoro-2-butene; 1-Chloro-1,1,2,4,4,4-hexafluoro-2-butene; 2-Chloro-1,3,3,3-Tetrafluoroprop-1-ene; 1,1,3,3,3-Pentafluoroprop-1-ene; 2-Chloro-1,1,3,3,3-pentafluoroprop-1-ene; Trifluoroacetone; Trifluoropropyne; and 1,1,4,4,4-Pentafluoro-1-butene, The composition contains more than about 95 mol% HFB.

42. A composition prepared by the system according to any one of claims 26 to 31 or the method according to any one of claims 36 to 39, the composition comprising: i)(Z)-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz); and ii) One or more additional compounds, said additional compounds being selected from the group consisting of: 1,1,1,3,3,3-Hexafluoropropane; (E)-1,1,1,4,4,4-hexafluorobutene; 1,1,1,2,2,4,4,4-octafluorobutane; 1,2-Dichloro-1,1,2,2-Tetrafluoroethane; 3-Chloro-1,1,1-trifluoropropane; 4-Chloro-1,1,1,2,2-pentafluorobutane; 2-Chloro-1,1,1,2,4,4,4-heptafluorobutane; 2-Chloro-1,1,1,3,4,4,4-heptafluorobutane; 2-Chloro-1,1,1,3,3-pentafluoropropane; 1-Chloro-1,1,3,3,3-pentafluoropropane; 2-Chloro-1,1,1,4,4,4-Hexafluorobutane; 1,2-Dichloro-1,1,3,3,3-pentafluoropropane; 1,2-Dichloro-3,3,3-trifluoroprop-1-ene; 1-Chloro-3,3,3-trifluoropropene; 1-Chloro-1,1,2,4,4,4-hexafluoro-2-butene; 1-Chloro-1,1,4,4,4-pentafluorobutane; 2-Chloro-1,1,1,3-Tetrafluoropropane; 1,1,1,3,3-Pentafluoropropane; (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and (E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene The composition contains more than about 99 mol% of Z-HFO-1336mzz.

Images