Compositions for producing chlorofluoroalkenes

Abstract

To provide a composition for a highly selective process for the production of 1224yd(Z) that is less expensive and causes less waste.SOLUTION: Provided is a composition comprising: a. (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)); and b. one of member (A) and member (B), wherein the member (A) includes one or more compounds selected from the group consisting of (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-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), and (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), and the member (B) includes one or more compounds 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-chloro-2,3,3,3-tetrafluoropropane (HCFC-244eb), and 1,1,1,2,3-pentafluoropropane (HFC-245eb).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 the Invention) The present invention is directed to a process for making hydrofluorocarbons. 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 Art

[0003] Hydrofluorocarbons (HFCs) such as HFC-134a and HFC-245fa have in recent years been used as alternatives to 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, dispersing media, buffing abrasives, replacement desiccants, and power cycle working fluids. HFCs do not contribute to stratospheric ozone depletion, but are a concern because they contribute to the "greenhouse effect," i.e., global warming. Because of their contribution to global warming, HFCs have also come under intense scrutiny and their widespread use is restricted. Thus, there is a need for compositions that do not contribute to stratospheric ozone depletion and also have a low global warming potential (GWP).

[0004] International Publication No. 2011 / 162341 (A1) describes a gas phase process for producing HCFO-1224yd as an intermediate in a gas phase process for producing HCFO-1234yf. This process uses hydrogen gas (H2) to hydrogenate HCFO-1214ya in the presence of a catalyst.

[0005] International Publication No. WO 2017 / 110851 (A1) describes a liquid-phase process for producing HCFO-1224yd. This process forms 1224yd in the presence of a catalyst using a basic solution such as KOH to dehydrochlorinate HCFC-234bb. The starting material 234bb is produced by chlorination of 1234yf, which is an expensive material. This process generates a large amount of aqueous waste. The 1224yd product produced from this process contains 5.5% - 6.4% of the 1224yd(E) isomer. The 1224yd(Z) isomer is a desirable product for many applications. The 1224yd(E) produced in this process requires further treatment to isomerize to the desired 1224yd(Z) isomer. This process can generate a large amount of waste that requires a large amount of disposal cost. The content thereof is hereby incorporated by reference in its entirety.

[0006] The disclosure of the international publication already specified is hereby incorporated by reference in this specification.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] Therefore, a highly selective process for producing 1224yd(Z) that is not so expensive and generates less waste is needed.

Means for Solving the Problems

[0009] The present invention can solve problems associated with conventional practices by providing a method that includes a composition of the present invention and a selective process for generating 1224(yd)(Z). "Selective" means 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 reagent to 1224(yd)(Z).

[0010] In one embodiment, a method for producing a chlorofluoroalkene, the 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, 3, a is an integer of 0, 1, 2, 3, y is independently an integer of 0, 1, 2, and z is an integer of 1, 2, 3) is contacted with hydrogen chloride (HCl) in the gas phase at a high temperature sufficient to effect hydrochlorination in the presence of an effective amount of a catalyst. The resulting reaction mixture is 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) (wherein x is an integer of 1, 2, 3, a is an integer of 0, 1, 2, 3, y is independently an integer of 0, 1, 2, m is an integer of 0, 1, n is an integer of 1, 2, p is an integer of 0, 1, and n + p is an integer of 1, 2) is included. In another embodiment, a method for producing a chlorofluoroalkene, the 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 with hydrogen chloride (HCl) in the gas phase at a high temperature sufficient to effect hydrochlorination in the presence of an effective amount of a catalyst. The resulting reaction mixture is 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) (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, 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) is included.

[0011] In another embodiment, a method for producing a chlorofluoroalkane, comprising contacting a reagent of formula (4) 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 gas phase at a high temperature sufficient to effect hydrochlorination in the presence of an effective amount of a catalyst. The resulting reaction mixture is 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) (including).

[0012] Another embodiment relates to any combination of the foregoing embodiments, wherein 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 selected from the group consisting 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 - 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 foregoing 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 foregoing embodiments, further comprising recovering the compound of formula (2) from the reaction mixture.

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

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

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

[0018] Another embodiment relates to any combination of the foregoing embodiments, wherein the catalyst is aluminum oxide (Al2O3), chromium oxide (Cr2O3), zinc-doped chromium oxide, or chromium oxide supported on aluminum oxide (Al2O3).

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

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

[0021] Another embodiment relates to any combination of the foregoing 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 foregoing embodiments, wherein the compound of formula (2) is (Z)-1-chloro-2,3,3,4,4,4-hexafluorobut-1-ene (HCFC-1326yd(Z)), (E)-1-chloro-2,3,3,4,4,4-hexafluorobut-1-ene (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 foregoing 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 reacting the compound of formula (5) with a dehydrohalogenation catalyst in the gas phase or with a caustic agent in the liquid phase to form a reaction mixture comprising the 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) (wherein x is an integer from 1, 2, 3, a is an integer from 0, 1, 2, 3, y is an integer from 0, 1, 2, y is independently 0, 1, or 2, m is an integer from 0, 1, n is an integer from 1, 2, p is an integer from 0, 1, and n + p is an integer from 1, 2) and contacting at a temperature high enough to form a reaction mixture comprising the same, and relates to any combination of the foregoing embodiments.

[0025] One embodiment relates to a composition comprising a composition produced by any combination of the foregoing 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 present invention relates to any combination of the foregoing 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 present invention relates to any combination of the foregoing 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 3-chloro-1,1,1,2,2-pentafluoropropane (HFC-235cb).

[0031] Another embodiment of the present invention relates to any combination of the foregoing 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-chloro-2,3,3,3-tetrafluoropropane (HCFC-244eb).

[0032] Another embodiment of the present invention relates to any combination of the foregoing 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-chloro-1,3,3,3-tetrafluoropropane (HCFC-244fa).

[0033] Another embodiment of the present invention relates to any combination of the foregoing 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 present invention relates to any combination of the foregoing 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 present invention relates to any combination of the foregoing 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 present invention relates to any combination of the foregoing 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 present invention relates to any combination of the foregoing 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 present invention relates to any combination of the foregoing 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 present invention relates to any combination of the foregoing 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 present invention relates to any combination of the foregoing 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] Embodiments of the present 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 INVENTION

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

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

[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 gas phase at a high temperature sufficient to effect hydrochlorination in the presence of an effective amount of a catalyst. The resulting reaction mixture is a linear or branched hydrochlorinated 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) (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, 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) comprises.

[0045] In one embodiment, the 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) (where 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, z is an integer of 1 or 2) is contacted with hydrogen chloride (HCl) in the gas phase at a high temperature sufficient to effect hydrochlorination in the presence of an effective amount of a catalyst. The resulting reaction mixture is a linear or branched hydrochlorinated 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) (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, 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) comprises.

[0046] In one embodiment, the reagent of formula (4) CF x H (3-x) (CF y H (2-y) ) a CF z H (3-z) , (4) (Wherein, 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 gas phase at a temperature high enough to effect hydrochlorination in the presence of an effective amount of a catalyst. The resulting reaction mixture is a linear or branched hydrochlorinated 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, 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) and contains

[0047] In one embodiment, the reagent 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) is contacted with a dehydrohalogenation catalyst in the gas phase or with a caustic agent in the liquid phase. The resulting reaction mixture is 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) (wherein 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, 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) comprises.

[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 mainly produces HCFO-1224yd(Z). HCFO-1224yd, as used herein, refers to the isomers, HCFO-1224yd(E) or HCFO-1224yd(Z), and 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] [Chemical Formula]

[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 primarily produces HCFO - 1224yd(Z). HCFO - 1224yd, as used herein, refers to the isomers, HCFO - 1224yd(E) or HCFO - 1224yd(Z), and 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]

Chemical formula

[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 primarily produces HCFO - 1224yd(Z). HCFO - 1224yd, as used herein, refers to the isomers, HCFO - 1224yd(E) or HCFO - 1224yd(Z), and 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]

Chemical formula

[0054] In some embodiments, 3-chloro-1,1,1,2,2-pentafluoropropane (HFC-235cb) may be recycled and returned to 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) can be converted to 1-chloro-2,3,3,3-tetrafluoropropene (Z / E) (HCFO-1224yd(Z / E)) by reacting with a caustic agent or by dehydrofluorination with a dehydrofluorination catalyst.

[0055] One embodiment includes 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. The reaction is shown below as Scheme (10).

[0056]

Chemical formula

[0057] The foregoing hydrochlorination reaction scheme can be carried out in the gas phase in a reaction zone containing a hydrochlorination catalyst at a temperature of about 150°C to about 500°C, about 175°C to about 400°C, about 200°C to about 350°C, and / or about 200°C to about 300°C. The contact time is typically about 1 to about 450 seconds and / or about 10 to about 120 seconds.

[0058] In some embodiments, suitable hydrogen chloride catalysts for use in the foregoing reaction scheme include gas-phase chromium or aluminum oxide catalysts. In one embodiment, the hydrogen chloride catalyst comprises aluminum oxide (Al2O3). In one embodiment, the hydrogen chloride catalyst comprises chromium oxide (Cr2O3). In one embodiment, the hydrogen chloride catalyst comprises chromium oxide supported on aluminum oxide. In one embodiment, the hydrogen chloride catalyst comprises zinc-doped chromium oxide. Suitable catalysts include, but are not limited to, chromium oxide, chromium oxyfluoride, chromium oxychloride, chromium halide, alumina, aluminum fluoride, aluminum fluoride oxide, metal compounds on aluminum fluoride, metal compounds on aluminum fluoride oxide; magnesium, zinc, and oxides, fluorides, and oxyfluorides of mixtures of magnesium and zinc and / or aluminum; lanthanum oxide and lanthanum oxyfluoride; carbon, acid-washed carbon, activated carbon, three-dimensional matrix carbonaceous materials; and metal compounds supported on carbon. The metal compound is an oxide, fluoride, and oxyfluoride 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 scheme can be less than atmospheric pressure, atmospheric pressure, or greater than atmospheric pressure. In one embodiment, the hydrogen chlorination is carried out at a pressure greater than atmospheric pressure (i.e., a pressure greater than 1 atm). In one embodiment, the hydrogen chlorination 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 component of the reaction mixture used in the foregoing reaction scheme 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 foregoing reaction scheme may optionally include additional gases. One or more additional gases may be added to extend the life of the catalyst. In some embodiments, the mole fraction of the additional gas based on the total gas is from about 0.1 mole percent to about 3 mole percent, from about 0.2 mole percent to about 2 mole percent, from about 0.5 mole percent to about 1.5 mole percent, from about 1 mole percent to about 1.5 mole percent, from about 1.5 mole percent to about 2 mole percent, from about 2 mole percent to about 3 mole percent, or from about 2.2 mole percent to about 2.5 mole percent. In one embodiment, the additional gas includes oxygen (O2).

[0062] The additional gas used in the foregoing 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 the 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 also typically a catalyst suitable for the isomerization of HCFO-1224yd(Z) to HCFO-1224yd(E) and / or from HCFO-1224yd(E) to HCFO-1224yd(Z). To maintain an equilibrium concentration or a concentration of HCFO-1224yd(E) above the equilibrium concentration, HCFO-1224yd(E) may be returned to the reaction so as to reach or exceed the equilibrium concentration between the isomers, thereby suppressing further formation of HCFO-1224yd(E) and favoring the desired HCFO-1224yd(Z) isomer. In some embodiments, by returning HCFO-1224yd(E) to the reaction such that the concentration of HCFO-1224yd(E) exceeds the equilibrium concentration, a portion of HCFO-1224yd(E) can be isomerized to HCFO-1224yd(Z). 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, in order to increase the overall yield, intermediates such as HCFC-235cb and unreacted HFO-1225ye may be returned to the reaction. In 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 present invention can produce a composition comprising from about 7 to about 95 percent, optionally from about 40 to about 90 percent, of 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] In the application of the process of the present invention, the reactors, distillation columns, and their associated feed lines, effluent lines, and related units used must be constructed of materials resistant to hydrogen fluoride and hydrogen chloride. Typical materials for construction known in the field of fluorination include stainless steel (especially austenitic), well-known high-nickel alloys such as Monel(trademark) nickel-copper alloy, Hastelloy(trademark) nickel-based alloy, and Inconel(trademark) nickel-chromium alloy, etc., and copper-clad steel.

[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 instead of or in combination with 1,2,3,3,3-pentafluoropropene (HFO-1225ye) as a starting reagent for producing HCFO-1224yd.

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

Example

[0070] (Example 1) Hydrochlorination of HFO-1225ye to 1224yd with chromium oxide catalyst JM62-3 8 mL of 12-20 mesh Johnson Matthey chromium oxide catalyst 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 a temperature of 300 °C to 425 °C. Then, HCl and HFO-1225ye were fed to the reactor at atmospheric pressure. The reaction conditions are listed in Table 1 below. The gas stream from the reactor was analyzed by GC and GC-MS. The results of the test are also shown in Table 1. In this reaction, a higher conversion rate of HFO-1225ye and a better yield of 1224yd were obtained.

[0071]

Table 1

[0072]

Table 2

[0073] (Example 2) Hydrogen Chlorination of 236ea to 1224yd with Chromium Oxide Catalyst JM62-3 8 mL of 12 - 20 mesh Johnson Matthey chromium oxide catalyst 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 a temperature of 300 °C - 425 °C. Then, HCl and 236ea were fed into the reactor at atmospheric pressure. The reaction conditions are listed in Table 2 below. The gas stream from the reactor was analyzed by GC and GC-MS. The test results are also shown in Table 2. In this reaction, a higher conversion rate of 236ea and a better yield of 1224yd were obtained.

[0074]

Table 3

[0075]

Table 4

[0076] (Example 3) Hydrogen Chlorination of 245eb with Chromium Oxide Catalyst JM62-3 After carrying out the reaction with 236ea in Example 1, the reactor was purged with N2 to remove the organic substances from the 236ea reactant. Then, HCl and 245eb were fed into the reactor at atmospheric pressure. The reaction conditions are listed in Table 3 below. The gas stream from the reactor was analyzed by GC and GC-MS. The test results are also shown in Table 3.

[0077]

Table 5

[0078]

Table 6

[0079]

Table 7

[0080] (Example 4) Hydrogen Chlorination of 236ea to 1224yd with BASF 4126 Al2O3 2 mL of 12 - 20 mesh BASF 4126 Al2O3 catalyst 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 a temperature of 300 °C - 425 °C. Then, HCl and 236ea were fed into the reactor at atmospheric pressure. The reaction conditions are listed in Table 3 below. The gas stream from the reactor was analyzed by GC and GC - MS. The results of the test are also shown in Table 4. 1224yd was produced in this reaction.

[0081]

Table 8

[0082]

Table 9

[0083] (Example 5) Hydrogen Chlorination of 236cb to 235cb and HCFO - 1224yd with Chromium Oxide Catalyst JM62 - 3 A 2 mL of 12 - 20 mesh Johnson Matthey chromium oxide catalyst 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 300 °C - 425 °C. Then, HCl and 236cb were fed into the reactor at atmospheric pressure. The reaction conditions are listed in Table 2 below. The gas stream from the reactor was analyzed by GC and GC - MS. The results of the tests are also shown in Table 5. In this reaction, a higher conversion rate of 236cb and better yields of 235cb and 1224yd were obtained.

[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 present invention and equivalents can be used in place of its elements. In addition, many modifications can be made without departing from the essential scope of the present invention to adapt a particular situation or material to the teachings of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed as the best mode contemplated for carrying out the present invention, but the present invention is intended to include all embodiments included within the scope of the appended claims. In addition, all numerical values specified in the detailed description shall be construed as if both exact and approximate values were explicitly specified.

Claims

1. a. (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)); b. one of member (A) and member (B); A composition comprising: Member (A) comprises one or more compounds selected from the group consisting of (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-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), and (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)); Member (B) comprises one or more compounds 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-chloro-2,3,3,3-tetrafluoropropane (HCFC-244eb), and 1,1,1,2,3-pentafluoropropane (HFC-245eb); A composition characterized by the above.

2. The composition according to claim 1, wherein member (A) comprises at least one of HCFO-1224yd(E), HFO-1225ye(Z), and HFO-1225ye(E).

3. The composition according to claim 1, wherein member (B) comprises at least one of HFC-236ea, HFC-236cb, and HFC-245eb.

4. The composition according to claim 1, further comprising 1,1,1,3,3-pentafluoropropane (HFC-245fa) or 1-chloro-1,3,3,3-tetrafluoropropane (HCFC-244fa).

5. The composition according to claim 2, containing HCFO-1224yd(Z) in an amount of 30 mol% to 90 mol%.

6. The composition according to claim 5, containing HCFO-1224yd(Z) in an amount of 40 mol% to 90 mol%.

7. The composition according to claim 2, characterized in that HCFO-1224yd(Z) and HCFO-1224yd(Z) are present in a total amount of from 32 mol% to 92 mol%.

8. The composition according to claim 1, characterized in that the composition comprises HCFO-1224yd(Z), HCFO-1224yd(E), HFO-1225ye(Z), HFO-1225ye(E), and further comprises 3-chloro-1,1,1,2,2-pentafluoropropane (HCFC-235cb).

9. The composition according to claim 1, characterized in that the composition comprises HCFO-1224yd(Z), HCFO-1233zd(Z), HCFO-1233zd(E), HCFC-244eb, 1-chloro-1,3,3,3-tetrafluoropropane (HCFC-244fa), 1,1,1,3,3-pentafluoropropane (HFC-245fa), or one of HFC-245eb, and 1,1,2-trichloro-2,3,3,3-tetrafluoropropane (HCFC-224ba).

10. The composition according to any one of claims 1 to 9, further comprising 1,3,3,3-tetrafluoropropene (HFO-1234ze), (Z)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), 1-chloro-2,3,3,3-tetrafluoropropane (HCFC-244eb), and 1,1,1,2,3-pentafluoropropane (HFC-245eb).

11. A fluid useful as a refrigerant, solvent, blowing agent, heat transfer medium or aerosol, characterized in that the fluid comprises the composition according to any one of claims 1 to 10.

12. The fluid according to claim 11, characterized in that it comprises from 40 mol% to 90 mol% of HCFO-1224yd(Z).

13. A composition further comprising 1,3,3,3 - tetrafluoropropene (HFO - 1234ze), (Z)-1 - chloro - 3,3,3 - trifluoropropene (HCFO - 1233zd(Z)), (E)-1 - chloro - 3,3,3 - trifluoropropene (HCFO - 1233zd(E)), 1 - chloro - 2,3,3,3 - tetrafluoropropane (HCFC - 244eb), and 1,1,1,2,3 - pentafluoropropane (HFC - 245eb).

14. The composition according to claim 13, further comprising 1,1,1,3,3 - pentafluoropropane (HFC - 245fa) or 1 - chloro - 1,3,3,3 - tetrafluoropropane (HCFC - 244fa).

15. A fluid useful as a refrigerant, solvent, blowing agent, heat transfer medium or aerosol, the fluid comprising the composition according to claim 13 or 14.

16. a. One of 1,2,3,3,4,4,4 - heptafluoro - 1 - butene (HFC - 1327cye) or 1,2,3,3,3 - pentafluoropropene (HFO - 1225ye); b. (i) At least one of (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)); c. At least one of (ii), (iii), or (iv), wherein the composition contains: (ii) is selected from at least one of 1,1,1,2,3,3 - hexafluoropropane (HFC - 236ea) and 1,1,1,2,2,3 - hexafluoropropane (HFC - 236cb), (iii) is 3 - chloro - 1,1,1,2,2 - pentafluoropropane (HFC - 235cb), and (iv) is selected from at least one of 1,2,2 - trichloro - 3,3,3 - trifluoropropane (HCFC - 233da) and 2 - chloro - 1,1,1,3,3 - pentafluoropropane (HFC - 235da). A composition characterized by the above.

17. The composition comprises HCFO-1224yd(Z) and HCFO-1224yd(E), and the HCFO-1225ye comprises (Z)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)) and (E)-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), the composition according to claim 16.

18. The composition comprises HCFO-1224yd(Z), HCFO-1224yd(E), HFO-1225ye(Z), and HFO-1225ye(E), and the composition further comprises at least one of (Z)-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd(Z)) and (E)-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd(E)), the composition according to claim 17.

19. The composition comprises HCFO-1224yd(Z), HCFO-1224yd(E), HFO-1225ye(Z), HFO-1225ye(E), and at least one of 1,2,2-trichloro-3,3,3-trifluoropropane (HCFC-233da) and 2-chloro-1,1,1,3,3-pentafluoropropane (HFC-235da), the composition according to claim 17.

20. The composition further comprises (Z)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), and 1,1,1,3,3-pentafluoropropane (HFC-245fa), the composition according to claim 16.

21. The composition according to claim 16, wherein HCFC-236cb, HCFC-235cb, HCFO-1224yd(Z), and HCFO-1224yd(E) are present.

22. The composition according to claim 16, further comprising 1,3,3,3 - tetrafluoropropene (HFC - 1234ze), (Z)-1 - chloro - 3,3,3 - trifluoropropene (HCFO - 1233zd(Z)), (E)-1 - chloro - 3,3,3 - trifluoropropene (HCFO - 1233zd(E)), 1 - chloro - 2,3,3,3 - tetrafluoropropane (HCFC - 244eb), and 1,1,1,2,3 - pentafluoropropane (HFC - 245eb).

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