Composition for producing chlorofluoroalkenes

Abstract

To provide a composition for a highly selective process for production of 1224yd(Z) that is less expensive and creates less waste.SOLUTION: A composition includes (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), and at least one of (E)-1,2-dichloro-3,3,3-trifluoropropene (HFO-1233xd(E)) and 2-chloro-1,3,3,3-tetrafluoropropene (HFO-1224xe).SELECTED DRAWING: None

Description

[Technical field]

[0001] This application claims the benefit of U.S. Application No. 62 / 718,255, filed Aug. 13, 2018. The disclosure of No. 62 / 718,255 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present invention is directed to a method for making hydrochlorofluorocarbons. In particular, the present invention is directed to a selective process for making chlorofluoroalkenes, such as 1-chloro-2,3,3,3-tetrafluoropropene (Z / E). [Background technology]

[0003] Hydrofluorocarbons (HFCs), such as HFC-134a and HFC-245fa, have been used in recent years as replacements for chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which can potentially damage the Earth's ozone layer. Hydrofluorocarbons (HFCs) have been used as effective refrigerants, fire extinguishing agents, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, dispersion media, buffing agents, displacement desiccants, and power cycle working fluids. HFCs are of concern because they do not contribute to the destruction of stratospheric ozone, but they do contribute to the "greenhouse effect," i.e., global warming. Because of their contribution to global warming, HFCs have also come under scrutiny and their widespread use has been restricted. Thus, there is a need for compositions that do not contribute to the destruction of stratospheric ozone and also have a low global warming potential (GWP).

[0004] WO 2011 / 162341(A1) describes a gas phase process for producing HCFO-1224yd as an intermediate in a gas phase process for producing HCFO-1234yf. The process uses hydrogen gas (H 2 O 4 ) to hydrogenate HCFO-1214ya in the presence of a catalyst. 2 ) is used.

[0005] WO 2017 / 110851(A1) describes a liquid phase process for producing HCFO-1224yd. The process uses a basic solution such as KOH to dehydrochlorinate HCFC-234bb to form 1224yd in the presence of a catalyst. The starting material 234bb was made by chlorination of 1234yf, an expensive material. The process generates large amounts of aqueous waste. The 1224yd product made from the process contains 5.5%-6.4% of the 1224yd(E) isomer. The 1224yd(Z) isomer is the desired product for many applications. The 1224yd(E) produced in the process requires further processing to isomerize to the desired 1224yd(Z) isomer. The process can generate large amounts of waste that require significant costs for disposal. The contents of which are incorporated herein by reference in their entirety.

[0006] The disclosures of the international publications previously identified are hereby incorporated by reference. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Application No. 62 / 718,255 [Patent Document 2] International Publication No. 2011 / 162341(A1) [Patent Document 3] International Publication No. 2017 / 110851(A1) Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, there is a need for a highly selective process for producing 1224yd(Z) that is less expensive and produces less waste. [Means for solving the problem]

[0009] The present invention can solve the problems associated with conventional practices by providing methods that include the compositions of the invention and selective processes for producing 1224(yd)(Z). By "selective" it is meant to refer to a process that converts at least about 30 percent, about 35 to about 40 percent, and in some cases more than 40 percent of the reagents to 1224(yd)(Z).

[0010] In one embodiment, a method for making a chlorofluoroalkene comprises the steps of: CF x H (3-x) (CF y H (2-y) ) a CF z H (3-z) , (1) wherein x is an integer of 1, 2, or 3, a is an integer of 0, 1, 2, or 3, y is independently an integer of 0, 1, or 2, and z is an integer of 1, 2, or 3, with hydrogen chloride (HCl) in the vapor phase in the presence of an effective amount of a catalyst at a temperature sufficient to effect hydrochlorination. The resulting reaction mixture is then reacted to produce a linear or branched compound of formula (2): CF x H (3-x) (CF y H (2-y) ) a-1 CF m H (1-m) =CCl n F p H (2-n-p) , (2) (In the formula, x is an integer of 1, 2, or 3; a is an integer of 0, 1, 2, or 3; y is independently an integer of 0, 1, or 2; m is an integer of 0 or 1; n is an integer of 1 or 2; p is an integer of 0 or 1; and n+p is an integer of 1 or 2. Includes. In another embodiment, a method for making a chlorofluoroalkene comprises the steps of: CF x H (3-x) (CF b H (2-b) ) a CF y H (1-y) =CF z H(2-z) , (3) wherein x is an integer of 1, 2, or 3, a is an integer of 0, 1, 2, or 3, b is independently an integer of 0, 1, or 2, y is independently an integer of 0 or 1, and z is an integer of 1 or 2, in the vapor phase, with hydrogen chloride (HCl) in the presence of an effective amount of a catalyst at a temperature sufficient to effect hydrochlorination. The resulting reaction mixture is then reacted to produce a linear or branched compound of formula (2): CF x H (3-x) (CF y H (2-y) ) a-1 CF m H (1-m) =CCl n F p H (2-n-p) , (2) (In the formula, x is an integer of 1, 2, or 3; a is an integer of 0, 1, 2, or 3; y is independently an integer of 0, 1, or 2; m is an integer of 0 or 1; n is an integer of 1 or 2; p is an integer of 0 or 1; and n+p is an integer of 1 or 2. Includes.

[0011] In another embodiment, a method for making a chlorofluoroalkane comprises the steps of: CF x H (3-x) (CF y H (2-y) ) a CF z H (3-z) , (4) wherein x is an integer from 1 to 3, a is an integer from 0 to 3, y is independently an integer from 0 to 2, and z is an integer from 1 to 3, with hydrogen chloride (HCl) in the vapor phase in the presence of an effective amount of a catalyst at a temperature sufficient to effect hydrochlorination. The resulting reaction mixture is then reacted to produce a linear or branched compound of formula (5): CF x H (3-x) (CF y H (2-y) ) a CCl v F (z-v) H (3-z) , (5) (wherein, y is independently an integer of 0, 1, or 2; v is independently an integer of 1 or 2; z is an integer of 1 or 2; and v is less than or equal to z). Includes.

[0012] Another embodiment is where the reagent of formula (1) is selected from the group consisting of 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,2,2,3-hexafluoropropane (HFC-236cb), 1,1,1,2,3-pentafluoropropane (HFC-245eb), and combinations thereof; and the compound of formula (2) is (Z)-1-chloro-2,3,3,3-tetrafluoropropane. any combination of the preceding embodiments, wherein the fluoropropene is selected from the group consisting of 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), and (E)-1-chloro-3,3,3-trifluoropropene (1233zd(E)).

[0013] Another embodiment relates to any combination of the preceding embodiments, wherein the compound of formula (2) comprises a mixture of (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)).

[0014] Another embodiment relates to any combination of the preceding embodiments, further comprising recovering the compound of formula (2) from the reaction mixture.

[0015] Another embodiment relates to any combination of the preceding embodiments, further comprising recycling at least a portion of the (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)) to the reaction.

[0016] Another embodiment relates to any combination of the preceding embodiments, further comprising recycling at least a portion of the 3-chloro-1,1,1,2,2-pentafluoropropane (HFC-235cb) produced back into the reaction.

[0017] Another embodiment relates to any combination of the preceding embodiments, wherein the catalyst is selected from the group consisting of chromium oxide, fluorinated chromium oxide, oxyfluorides of chromium, chromium halides, alumina, aluminum fluoride, alumina fluoride, metal compounds on aluminum fluoride, metal compounds on alumina fluoride; oxides, fluorides, and oxyfluorides of magnesium, zinc, and mixtures of magnesium and zinc and / or aluminum; lanthanum oxide and fluorinated lanthanum oxide; carbon, acid washed carbon, activated carbon, three dimensional matrix carbonaceous materials; metal compounds supported on carbon, and combinations thereof.

[0018] Another embodiment is where the catalyst is aluminum oxide (Al 2 O 3 ), chromium oxide (Cr 2 O 3 ), zinc-doped chromium oxide, or aluminum oxide (Al 2 O 3 3. The method of claim 1, wherein the chromium oxide is supported on a chromium-containing matrix.

[0019] Another embodiment relates to any combination of the preceding embodiments, wherein the molar ratio of hydrogen chloride to the sum of the moles of the reagent of formula (1) and the moles of the compound of formula (2) is from about 0.2:1 to about 10:1.

[0020] Another embodiment relates to any combination of the preceding embodiments, wherein the sufficiently high temperature to form the reaction mixture is between 150°C and 500°C.

[0021] Another embodiment relates to any combination of the preceding embodiments, wherein the reagent of formula (3) is 1,2,3,3,4,4,4-heptafluoro-1-butene, (HFC-1327cye) or 1,2,3,3,3-pentafluoropropene (HFO-1225ye).

[0022] Another embodiment relates to any combination of the preceding embodiments, wherein the compound of formula (2) is (Z)-1-chloro-2,3,3,4,4,4-hexafluoro-1-butene (HCFC-1326yd(Z)), (E)-1-chloro-2,3,3,4,4,4-hexafluoro-1-butene (HCFC-1326yd(E)), (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), or (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)).

[0023] Another embodiment relates to any combination of the preceding embodiments, wherein at least 90 percent of the reagent of formula (3) is converted to (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)).

[0024] Another embodiment is A compound of formula (5) is reacted with a dehydrohalogenation catalyst in the vapor phase or with a caustic agent in the liquid phase to produce a compound of formula (6) CF x H (3-x) (CF y H (2-y) ) a-1 CF m H (1-m) =CCl n F p H (2-n-p) , (6) (In the formula, x is an integer of 1, 2, or 3; a is an integer of 0, 1, 2, or 3; y is an integer of 0, 1, or 2, and y is independently 0, 1, or 2; m is an integer of 0 or 1; n is an integer of 1 or 2; p is an integer of 0 or 1, and n+p is an integer of 1 or 2. any combination of the preceding embodiments, further comprising contacting at a sufficiently elevated temperature to form a reaction mixture comprising:

[0025] One embodiment relates to compositions, including compositions produced by any combination of the aforementioned processes.

[0026] Another embodiment relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), and (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)).

[0027] Another embodiment relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), and 1,1,1,2,3,3-hexafluoropropane (HFC-236ea).

[0028] Another embodiment relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), and 1,1,1,2,2,3-hexafluoropropane (HFC-236cb).

[0029] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), 3-chloro-1,1,1,2,2-pentafluoropropane (HFC-235cb), and 1,1,1,2,2,3-hexafluoropropane (HFC-236cb).

[0030] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), and (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), and 3-chloro-1,1,1,2,2-pentafluoropropane (HFC-235cb).

[0031] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), and (E)-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and 1-chloro-2,3,3,3-tetrafluoropropane (HCFC-244eb).

[0032] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), and (E)-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and 1-chloro-1,3,3,3-tetrafluoropropane (HCFC-244fa).

[0033] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), and (E)-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and 1,1,1,3,3-pentafluoropropane (HFC-245fa).

[0034] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), and (E)-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and 1,1,1,2,3-pentafluoropropane (HFC-245eb).

[0035] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), and (E)-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and 1,1,2-trichloro-2,3,3,3-tetrafluoropropane (HCFC-224ba).

[0036] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), (Z)-1,2-dichloro-3,3,3-trifluoropropene (1223xd(Z)), and (E)-1,2-dichloro-3,3,3-trifluoropropene (1223xd(E)).

[0037] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), and 1,1,1,2,2,3-hexafluoropropane (HFC-236cb).

[0038] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), (E)-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and 1,1,1,3,3-pentafluoropropane (HFC-245fa).

[0039] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises 1,1,1,2,2,3-heptafluoropropane (HFC-236cb), 3-chloro-1,1,1,2,2-pentafluoropropane (HFC-235cb), (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), and (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)).

[0040] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the composition comprises 1,3,3,3-tetrafluoropropene (HFC-1234ze), (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), (E)-1-chloro-3,3,3-trifluoropropene (1233zd(E)), 1-chloro-2,3,3,3-tetrafluoropropane (HCFC-244eb), and 1,1,1,2,3-pentafluoropropane (HFC-245eb).

[0041] The embodiments of the invention can be used alone or in combination with each other. Other features and advantages of the present invention will become apparent from the following more detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] The present invention provides a gas phase process for the hydrochlorination of chlorofluoroalkanes, fluorinated alkanes, and fluorinated alkenes to form chloroalkanes, chlorofluoroalkanes, chlorofluoroalkenes, and chloroalkenes. The present invention further provides for the conversion of chlorofluoroalkanes to chlorofluoroalkenes.

[0043] The present invention further provides compounds such as 1-chloro-2,3,3,3-tetrafluoropropene (1224yd), which have low global warming potential (GWP) and are useful as cleaning agents, refrigerants, blowing agents, solvents, and aerosols.

[0044] In one embodiment, a reagent of formula (1) CF x H (3-x) (CF y H (2-y) ) a CF z H (3-z) , (1) (wherein x is an integer of 1, 2, or 3, a is an integer of 0, 1, 2, or 3, y is independently an integer of 0, 1, or 2, and z is an integer of 1, 2, or 3) is contacted with hydrogen chloride (HCl) in the vapor phase in the presence of an effective amount of a catalyst at a temperature sufficient to effect hydrochlorination. The resulting reaction mixture contains linear or branched hydrochlorinated compounds of formula (2): CF x H (3-x) (CF y H (2-y) ) a-1 CF m H (1-m) =CCl n F p H (2-n-p) , (2) (In the formula, x is an integer of 1, 2, or 3; a is an integer of 0, 1, 2, or 3; y is independently an integer of 0, 1, or 2; m is an integer of 0 or 1; n is an integer of 1 or 2; p is an integer of 0 or 1; and n+p is an integer of 1 or 2. Includes.

[0045] In one embodiment, a reagent of formula (3) CF x H (3-x) (CF b H (2-b) ) a CF y H (1-y) =CF z H (2-z) , (3) wherein x is an integer of 1, 2, or 3, a is an integer of 0, 1, 2, or 3, b is independently an integer of 0, 1, or 2, y is independently an integer of 0 or 1, and z is an integer of 1 or 2, is contacted in the vapor phase with hydrogen chloride (HCl) in the presence of an effective amount of a catalyst at a temperature sufficient to effect hydrochlorination. The resulting reaction mixture contains linear or branched hydrochlorinated compounds of formula (2): CF x H (3-x) (CF y H (2-y) ) a-1 CF m H (1-m) =CCl n F p H (2-n-p) , (2) (In the formula, x is an integer of 1, 2, or 3; a is an integer of 0, 1, 2, or 3; y is independently an integer of 0, 1, or 2; m is an integer of 0 or 1; n is an integer of 1 or 2; p is an integer of 0 or 1; and n+p is an integer of 1 or 2. Includes.

[0046] In one embodiment, a reagent of formula (4) CF x H (3-x) (CF y H (2-y) ) a CF z H (3-z) , (4) where x is an integer of 1, 2, or 3, a is an integer of 0, 1, 2, or 3, y is an integer of 0, 1, or 2, and z is an integer of 1, 2, or 3, is contacted with hydrogen chloride (HCl) in the vapor phase in the presence of an effective amount of a catalyst at a temperature high enough to effect hydrochlorination. The resulting reaction mixture contains linear or branched hydrochlorinated compounds of formula (5): CF x H (3-x) (CF y H (2-y) ) a CCl v F (z-v) H (3-z) , (5) (wherein x is an integer of 1, 2, or 3; a is an integer of 0, 1, 2, or 3; y is independently an integer of 0, 1, or 2; v is an integer of 1 or 2; z is an integer of 1 or 2, and v is less than or equal to z). Includes.

[0047] In one embodiment, a reagent of formula (5) CF x H (3-x) (CF y H (2-y) ) a CCl v F (z-v) H (3-z) , (5) where x is an integer of 1, 2, or 3, a is an integer of 0, 1, 2, or 3, y is independently an integer of 0, 1, or 2, v is an integer of 1 or 2, z is an integer of 1 or 2, and v is less than or equal to z, is contacted in the vapor phase with a dehydrohalogenation catalyst or in the liquid phase with a caustic agent. The resulting reaction mixture is reacted to produce a compound of formula (6): CF x H (3-x) (CF y H (2-y) ) a-1 CF m H (1-m) =CCl n F p H (2-n-p) , (6) (In the formula, x is an integer of 1, 2, or 3; a is an integer of 0, 1, 2, or 3; y is an integer of 0, 1, or 2, and y is independently 0, 1, or 2; m is an integer of 0 or 1; n is an integer of 1 or 2; p is an integer of 0 or 1, and n+p is an integer of 1 or 2. Includes.

[0048] One embodiment includes a gas phase process for converting 1,2,3,3,3-pentafluoropropene (HFO-1225ye) to 1-chloro-2,3,3,3-tetrafluoropropene (Z / E) (HCFO-1224yd(Z / E)). HCFO-1224yd(Z / E) is produced in a highly selective process that produces primarily HCFO-1224yd(Z). HCFO-1224yd, as used herein, refers to the isomers HCFO-1224yd(E) or HCFO-1224yd(Z), as well as any combination or mixture of such isomers. The conversion of 1,2,3,3,3-pentafluoropropene (HFO-1225ye) to 1-chloro-2,3,3,3-tetrafluoropropene (Z / E) (HCFO-1224yd(Z / E)) is shown in Scheme (7).

[0049] [ka]

[0050] One embodiment includes a gas phase process for converting 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) to 1-chloro-2,3,3,3-tetrafluoropropene (Z / E) (HCFO-1224yd(Z / E)). HCFO-1224yd(Z / E) is produced in a highly selective process that produces primarily HCFO-1224yd(Z). HCFO-1224yd, as used herein, refers to the isomers HCFO-1224yd(E) or HCFO-1224yd(Z), as well as any combination or mixture of such isomers. The conversion of 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) to 1-chloro-2,3,3,3-tetrafluoropropene (Z / E) (HCFO-1224yd(Z / E)) is shown in Scheme (8).

[0051] [ka]

[0052] One embodiment includes a gas phase process for converting 1,1,1,2,2,3-hexafluoropropane (HFC-236cb) to 1-chloro-2,3,3,3-tetrafluoropropene (Z / E) (HCFO-1224yd(Z / E)). HCFO-1224yd(Z / E) is produced in a highly selective process that produces primarily HCFO-1224yd(Z). HCFO-1224yd, as used herein, refers to the isomers HCFO-1224yd(E) or HCFO-1224yd(Z), as well as any combination or mixture of such isomers. The conversion of 1,1,1,2,2,3-hexafluoropropane (HFC-236cb) to 1-chloro-2,3,3,3-tetrafluoropropene (Z / E) (HCFO-1224yd(Z / E)) is shown in Scheme (9).

[0053] [ka]

[0054] In some embodiments, 3-chloro-1,1,1,2,2-pentafluoropropane (HFC-235cb) may be recycled back into the reaction for further conversion to 1-chloro-2,3,3,3-tetrafluoropropene (Z / E) (HCFO-1224yd(Z / E)). In some embodiments, 3-chloro-1,1,1,2,2-pentafluoropropane (HFC-235cb) may be converted to 1-chloro-2,3,3,3-tetrafluoropropene (Z / E) (HCFO-1224yd(Z / E)) by reaction with a caustic agent or by dehydrofluorination with a dehydrofluorination catalyst.

[0055] One embodiment involves a gas phase process for converting 1,1,1,2,3-pentafluoropropane (HFC-245eb) to 1-chloro-3,3,3-trifluoropropene (1233zd) by a hydrochlorination reaction, which is shown below as Scheme (10).

[0056] [ka]

[0057] The foregoing hydrochlorination reaction schemes may be carried out in the gas phase in a reaction zone containing a hydrochlorination catalyst at temperatures of from about 150° C. to about 500° C., from about 175° C. to about 400° C., from about 200° C. to about 350° C., and / or from about 200° C. to about 300° C. Contact times are typically from about 1 to about 450 seconds and / or from about 10 to about 120 seconds.

[0058] In some embodiments, a hydrochlorination catalyst suitable for use in the foregoing reaction scheme comprises a gas-phase chromium or aluminum oxide catalyst. In one embodiment, the hydrochlorination catalyst comprises aluminum oxide (Al 2 O 3 In one embodiment, the hydrochlorination catalyst comprises chromium oxide (Cr 2 O 3). In one embodiment, the hydrochlorination catalyst comprises chromium oxide supported on aluminum oxide. In one embodiment, the hydrochlorination catalyst comprises zinc doped chromium oxide. Suitable catalysts include, but are not limited to, chromium oxide, fluorinated chromium oxide, oxyfluorides of chromium, chromium halides, alumina, aluminum fluoride, alumina fluoride, metal compounds on aluminum fluoride, metal compounds on alumina fluoride; oxides, fluorides, and oxyfluorides of magnesium, zinc, and mixtures of magnesium and zinc and / or aluminum; lanthanum oxide and lanthanum oxide fluoride; carbon, acid washed carbon, activated carbon, three-dimensional matrix carbonaceous materials; and metal compounds supported on carbon. The metal compounds are oxides, fluorides, and oxyfluorides of at least one metal selected from the group consisting of sodium, potassium, rubidium, cesium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, chromium, iron, cobalt, rhodium, nickel, copper, zinc, and mixtures thereof. The catalyst is contacted for a time sufficient to affect the desired reaction scheme.

[0059] The reaction pressure used in the foregoing reaction schemes can be subatmospheric, atmospheric, or superatmospheric. In one embodiment, the hydrochlorination is carried out at superatmospheric pressure (i.e., pressure greater than 1 atmosphere). In one embodiment, the hydrochlorination is carried out at substantially atmospheric pressure. In some embodiments, the reaction can be carried out at a pressure of 0 to 100, 0 to 50, 0 to 30, 1 to 25, 5 to 20, or 7 to 15 pounds per square inch gauge (psig).

[0060] The molar ratio of hydrogen chloride to the organic components of the reaction mixture used in the foregoing reaction schemes can be from about 0.2:1 to about 10:1, from about 0.3:1 to about 5:1, or from about 0.4:1 to about 2:1.

[0061] The catalytic hydrochlorination of the above reaction scheme may optionally include an additional gas. One or more additional gases may be added to extend the life of the catalyst. In some embodiments, the molar fraction of the additional gas based on the total gas is from about 0.1 molar percent to about 3 molar percent, from about 0.2 molar percent to about 2 molar percent, from about 0.5 molar percent to about 1.5 molar percent, from about 1 molar percent to about 1.5 molar percent, from about 1.5 molar percent to about 2 molar percent, from about 2 molar percent to about 3 molar percent, or from about 2.2 molar percent to about 2.5 molar percent. In one embodiment, the additional gas is oxygen (O 2 ).

[0062] The additional gas used in the above reaction scheme may include one or more inert gases. In some embodiments, the reaction is carried out under nitrogen, helium, and / or argon. In some embodiments, the gas used as the reactor atmosphere may be pre-dried to remove substantially all water. In one embodiment, the reaction is carried out under dry nitrogen.

[0063] The effluent from the reaction zone of a gas phase fluorination reactor typically contains one or more of HCl, HF, HCFO-1224yd, HCFC-235cb, HFC-236ea, HFC-236cb, 1223xd, and HFO-1225ye.

[0064] The desired HCFO-1224yd(Z) and its mixture with HF can be separated from the reaction mixture by methods known in the art (e.g., distillation). The catalyst used in the hydrochlorination reaction is typically also a catalyst suitable for the isomerization of HCFO-1224yd(Z) to HCFO-1224yd(E) and / or HCFO-1224yd(E) to HCFO-1224yd(Z). To maintain a concentration of HCFO-1224yd(E) at or above the equilibrium concentration, HCFO-1224yd(E) may be returned to the reaction to reach or exceed the equilibrium concentration between the isomers, thereby suppressing further formation of HCFO-1224yd(E) in favor of the desired HCFO-1224yd(Z) isomer. In some embodiments, a portion of the HCFO-1224yd(E) may be isomerized to HCFO-1224yd(Z) by returning HCFO-1224yd(E) to the reaction such that the concentration of HCFO-1224yd(E) exceeds the equilibrium concentration. In some embodiments, this results in an overall selectivity for the HCFO-1224yd(Z) isomer of greater than 90 percent, greater than 92 percent, greater than 95 percent, and / or greater than 97 percent.

[0065] In some embodiments, intermediates such as HCFC-235cb and unreacted HFO-1225ye may be returned to the reaction to increase the overall yield, hi some embodiments, the overall conversion of HFO-1225ye to HCFO-1224yd(Z) may be greater than 80 percent, greater than 85 percent, and / or greater than 90 percent.

[0066] In one embodiment, the process of the invention can produce a composition comprising from about 7 to about 95 percent, and in some cases, from about 40 to about 90 percent, HCFO-1224(yd)(Z), with the remainder comprising at least one additional compound selected from the group consisting of 1225ye(Z), 1225ye(E), and 236cb. The additional compound having a lower boiling point than HCFO-1224(yd)(Z) can impart improved refrigeration performance.

[0067] The reactors, distillation columns and their associated feed and bleed lines, as well as related units used in the application of the process of the present invention must be constructed of materials resistant to hydrogen fluoride and hydrogen chloride.Typical materials of construction well known in the field of fluorination include stainless steels (especially austenitic), well known high nickel alloys such as Monel™ nickel-copper alloys, Hastelloy™ nickel-based alloys, and Inconel™ nickel-chromium alloys, as well as copper-clad steels.

[0068] In an alternative embodiment, 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and / or 1,1,1,2,2,3-hexafluoropropane (HFC-236cb) may be used in place of or in combination with 1,2,3,3,3-pentafluoropropene (HFO-1225ye) as starting reagents to produce HCFO-1224yd.

[0069] The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0070] Example 1 Hydrochlorination of HFO-1225ye to 1224yd over chromium oxide catalyst JM62-3 8 mL of 12-20 mesh Johnson Matthey chromium oxide catalyst was loaded into a ½ inch Hastelloy C 227 reactor. The catalyst was dried at 250° C. for 2 hours and then activated by HF treatment at temperatures between 300° C. and 425° C. HCl and HFO-1225ye were then fed to the reactor at atmospheric pressure. The reaction conditions are listed in Table 1 below. The air stream from the reactor was analyzed by GC and GC-MS. The results of the test are also shown in Table 1. This reaction gave higher conversion of HFO-1225ye and better yield of 1224yd.

[0071] [Table 1]

[0072] [Table 2]

[0073] Example 2 Hydrochlorination of 236ea to 1224yd over chromium oxide catalyst JM62-3 8 mL of 12-20 mesh Johnson Matthey chromium oxide catalyst was loaded into a ½ inch Hastelloy C 227 reactor. The catalyst was dried at 250° C. for 2 hours and then activated by HF treatment at temperatures between 300° C. and 425° C. HCl and 236ea were then fed to the reactor at atmospheric pressure. The reaction conditions are listed in Table 2 below. The air stream from the reactor was analyzed by GC and GC-MS. The results of the test are also shown in Table 2. This reaction gave a higher conversion of 236ea and a better yield of 1224 yd.

[0074] [Table 3]

[0075] [Table 4]

[0076] Example 3 Hydrochlorination of 245eb over chromium oxide catalyst JM62-3 After carrying out the reaction with 236ea in Example 1, the reactor was purged with N2 to remove organics from the 236ea reaction. HCl and 245eb were then fed to the reactor at atmospheric pressure. The reaction conditions are listed in Table 3 below. The air stream from the reactor was analyzed by GC and GC-MS. The results of the tests are also shown in Table 3.

[0077] [Table 5]

[0078] [Table 6]

[0079] [Table 7]

[0080] Example 4 Hydrochlorination of 236ea to 1224yd with BASF 4126 Al2O3 2 mL of BASF 4126 Al2O3 catalyst, 12-20 mesh, was loaded into a 1 / 2 inch Hastelloy C 227 reactor. The catalyst was dried at 250°C for 2 hours and then activated by HF treatment at temperatures between 300°C and 425°C. HCl and 236ea were then fed to the reactor at atmospheric pressure. The reaction conditions are listed in Table 3 below. The air stream from the reactor was analyzed by GC and GC-MS. The results of the test are also shown in Table 4. 1224 yd was produced in this reaction.

[0081] [Table 8]

[0082] [Table 9]

[0083] Example 5 Hydrochlorination of 236cb to 235cb and HCFO-1224yd over chromium oxide catalyst JM62-3 2 mL of 12-20 mesh Johnson Matthey chromium oxide catalyst was loaded into a ½ inch Hastelloy C 227 reactor. The catalyst was dried at 250° C. for 2 hours and then activated by HF treatment at 300° C.-425° C. HCl and 236cb were then fed to the reactor at atmospheric pressure. The reaction conditions are listed in Table 2 below. The air stream from the reactor was analyzed by GC and GC-MS. The results of the test are also shown in Table 5. This reaction gave higher conversion of 236cb and better yield of 235cb and 1224yd.

[0084] [Table 10]

[0085] [Table 11]

[0086] Although the present invention has been described with reference to one or more embodiments, it will be understood by those skilled in the art that various changes can be made without departing from the scope of the invention and that equivalents can be substituted for the elements. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope of the invention. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but the invention is intended to include all embodiments falling within the scope of the appended claims. In addition, all numerical values ​​specified in the detailed description should be interpreted as if both exact and approximate values ​​were explicitly specified.

Claims

1. A composition comprising at least one of (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), and (E)-1,2-dichloro-3,3,3-trifluoropropene (HFO-1223xd(E)) and 3-chloro-1,1,1,2,2-pentafluoropropene (HCFC-235cb).

2. A composition comprising (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), and at least one of (E)-1,2-dichloro-3,3,3-trifluoropropene (HFO-1223xd(E)) and 2-chloro-1,3,3,3-tetrafluoropropene (HFO-1224xe).

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