Integrated process for making fluorinated olefins

Abstract

The invention relates to an integrated process for making fluorinated olefins. The present invention relates, at least in part, to a method for increasing the cost efficiency of a dehydrohalogenation production process of fluorinated olefins by recovering and recycling a spent dehydrohalogenation agent. In one aspect, the invention relates to dehydrohalogenating fluorinated alkanes (e.g., pentafluoropropane and / or hexafluoropropane) in the presence of a dehydrohalogenating agent to produce fluorinated alkenes (e.g., tetrafluoropropene and / or pentafluoropropene). Removal of the spent dehydrohalogenating agent from the reactor makes the organic matter readily separated from the dehydrohalogenating agent, the latter being recycled.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a divisional application of the invention patent application with the application date of October 7, 2011, application number 202111058499.8, and the name is "Integrated process for making fluorinated olefins". The application with application number 202111058499.8 is a divisional application of the invention patent application with the application date of October 7, 2011, application number 201711048814.2, and the name is "Integrated process for making fluorinated olefins". The application with application number 201711048814.2 is a divisional application of the invention patent application with the application date of October 7, 2011, application number 201180059852.2, and the name is "Integrated process for making fluorinated olefins". This application is related to and claims priority to U.S. Provisional Application No. 61 / 392,242 filed on October 12, 2010, the contents of which are incorporated herein by reference.

[0002] This application is also a continuation-in-part of U.S. application serial number 13 / 195,429, filed on August 1, 2011, which is a continuation of U.S. patent application serial number 12 / 402,372 (now U.S. Patent No. 8,013,194), filed on March 11, 2009, which in turn claims priority to U.S. Provisional Patent Application No. 61 / 036,526, filed on March 14, 2008, each of which is incorporated herein by reference. Technical Field

[0003] The present invention relates to a process for producing halogenated olefins, particularly, but not limited to, 2,3,3,3-tetrafluoropropane (HFO-1234yf) and / or 1,2,3,3,3-pentafluoropropene (HFO-1225ye). Background Art

[0004] Chlorine-containing compounds, such as chlorofluorocarbons (CFCs), have been used as refrigerants, foaming agents, cleaning agents, solvents, heat transfer media, disinfectants, aerosol propellants, dielectrics, fire extinguishing agents and power cycle working fluids. Such chlorine-containing compounds are proven to be harmful to the Earth's ozone layer. Many hydrofluorocarbons (HFCs) used as substitutes for CFCs have been found to contribute to global warming. For these reasons, global efforts have been made to develop more environmentally friendly and effective or more effective novel compounds from a performance perspective simultaneously.

[0005] Applicants have recognized that 1,1,1,2,3-pentafluoropropene (HFO-1225ye) and 1,1,1,2-tetrafluoropropene (HFO-1234yf) are each useful for one or more of the above-mentioned uses. Thus, compositions containing either or both of these fluorinated olefins are among the materials developed for such uses.

[0006] Methods for making HFO-1234yf and HFO-1225ye are known. In one example, hexafluoropropylene (HFP) is known to be hydrogenated to produce 1,1,1,2,3,3-hexafluoropropane (HFC-236ea). HFC-236ea is then used as a reactant in a dehydrogenation reaction to make HFO-1225ye. It is also known that HFO-1225ye can be hydrogenated to produce 1,1,1,2,3-pentafluoropropane (HFC-245eb) and HFC-245eb can then be dehydrofluorinated to produce HFO-1234yf.

[0007] U.S. Patent Application Publication No. 2009 / 0234165 (the contents of which are incorporated herein by reference) further suggests that HFO-1225ye and HFO-1234yf can be produced in a single facility. Most notably, it is recognized that the hydrogenation of HFP can produce HFC-236ea and HFC-245eb, and these two products can be simultaneously dehydrofluorinated to produce HFO-1225ye and HFO-1234yf, respectively. Processing conditions are taught to be adjustable to favor the selective conversion of one hydrofluoroolefin over another. Catalysts that can be used for such reactions are taught to include metal catalysts, and further preferably one or more transition metal-based catalysts (including transition metal halide catalysts in certain preferred embodiments), such as supported or bulk FeCl3, chromium oxyfluoride, Ni (including Ni mesh), NiCl2, CrF3, and mixtures thereof. Other catalysts include carbon-supported catalysts, antimony-based catalysts (such as SbCl5), aluminum-based catalysts (such as AlF3, Al2O3 and fluorinated Al2O3), palladium-based catalysts, platinum-based catalysts, rhodium-based catalysts and ruthenium-based catalysts, including combinations thereof.

[0008] Other examples of methods for making HFO-1225ye and HFO-1234yf are described in at least U.S. Pat. No. 7,560,602, assigned to the assignee of the present invention and incorporated herein by reference. This patent discloses a similar dehydrohalogenation process for making 2,3,3,3-tetrafluoropropene (1234yf) and 1,1,1,2,3-pentafluoropropene (HFO-1225ye) by catalytic dehydrofluorination of 1,1,1,2,3-pentafluoropropane (245eb) and 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), respectively. Preferred dehydrohalogenation catalysts include fluorinated chromium oxide catalysts, aluminum fluoride catalysts, iron fluoride catalysts, mixtures of magnesium fluoride and aluminum fluoride catalysts, nickel-based catalysts, carbon-based catalysts, and combinations thereof.

[0009] Optional reagents for such dehydrohalogenation reactions are also known. U.S. Patent Application Publication No. 20100029997, for example, teaches the production of hydrogenated olefins (e.g., HFO-1234yf) by contacting HFC-245eb with potassium hydroxide (KOH), sodium hydroxide (NaOH), Ca(OH)2, CaO, and combinations thereof to dehydrohalogenate HFC-245eb. In certain embodiments, the dehydrohalogenation agent includes KOH, and the optional reagents also include LiOH, Mg(OH)2, and NaOH.

[0010] Applicants have recognized that in continuous processing using such dehydrohalogenating agents (also referred to as "reagents"), the reaction proceeds until the organic reactants or dehydrohalogenating agent are exhausted. After the reaction is complete, the reactor must be disassembled to remove salts and / or salt solutions. This in turn results in higher operating costs and reduced productivity. Therefore, a more effective method is needed to remove spent reagents and recycle unused or regenerated reagents and / or unused organic matter in a continuous process.

[0011] Applicants believe that the present invention addresses the above needs. Summary of the invention

[0012] The present invention relates, at least in part, to methods for improving the cost efficiency of a dehydrohalogenation process for producing fluorinated olefins by recovering and recycling spent reagents. In one aspect, the present invention relates to dehydrohalogenating fluorinated alkanes (e.g., pentafluoropropane and / or hexafluoropropane) in the presence of a dehydrohalogenation agent to produce fluorinated olefins (e.g., tetrafluoropropene and / or pentafluoropropene). Such dehydrohalogenation agents may include, but are not limited to, potassium hydroxide (KOH), sodium hydroxide (NaOH), calcium hydroxide (Ca(OH)2), lithium hydroxide (LiOH), magnesium hydroxide (Mg(OH)2), calcium oxide (CaO), or combinations thereof. Removal of spent dehydrohalogenation agents from the reactor allows for easy separation of organics from the dehydrohalogenation agent. This in turn results in lower costs associated with the design and operation of complex and highly specialized separation equipment. Recycling of spent dehydrohalogenation agents results in higher efficiencies. Improved productivity is similarly observed if metal fluoride salts are also separated from the product stream, converted back to the original form of the dehydrohalogenation agent, and recycled to the reaction.

[0013] In one aspect, the present invention relates to a method or process for making fluorinated olefins, comprising: (a) hydrogenating a first halogenated olefin to produce a halogenated alkane; (b) optionally separating the halogenated alkane into a plurality of intermediate product streams, including two or more streams selected from a first stream rich in at least a first alkane, a second stream rich in a second alkane, and an alkane recycle stream; (c) dehydrohalogenating the halogenated alkane in (a) or (b) in the presence of a dehydrohalogenating agent to produce a second halogenated olefin; (d) removing a reaction stream comprising a spent dehydrohalogenating agent and an optional metal fluoride salt by-product; and (e) recovering, purifying and / or regenerating the spent dehydrohalogenating agent. The first halogenated olefin may comprise a compound of formula (I): (CX n Y 3-n )(CR 1 a R 2 b ) z CX=CH m X 2-m (I) wherein each X is independently Cl, F, I or Br, provided that at least two X are F; each Y is independently H, Cl, F, I or Br; each R 1 R2 is independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; each R2 is independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; n is 1, 2 or 3; a and b are each 0, 1 or 2, provided that a+b=2; m is 0, 1 or 2; and z is 0, 1, 2 or 3.

[0014] In further embodiments of the above, the first halogenated olefin comprises or consists of a compound of formula (IA): CX n Y 3-n CX=CH m X 2-m (IA) wherein each X is independently Cl, F, I or Br, provided that at least two X are F; each Y is independently H, Cl, F, I or Br; n is 1, 2 or 3; and m is 0, 1 or 2.

[0015] In still further embodiments of the above, the first halogenated alkane is hexafluoropropylene (HFP).

[0016] The first haloalkane of the reaction method can, in certain embodiments, be any compound of formula (II): (CX n Y 3-n )(CR 1 a R 2 b ) z CHXm+1 X 2-m (II) wherein each X is independently Cl, F, I or Br, provided that at least two X are F; each Y is independently H, Cl, F, I or Br; each R 1 R2 is independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; each R2 is independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; n is 1, 2 or 3; a and b are each 0, 1 or 2, provided that a+b=2; m is 0, 1 or 2; and z is 0, 1, 2 or 3.

[0017] In further embodiments of the above, the haloalkane is a compound of formula (IIA): (CX n Y 3-n )CHXCH m+1 X 2-m (IIA) wherein each X is independently Cl, F, I or Br, provided that at least two X are F; each Y is independently H, Cl, F, I or Br; n is 1, 2 or 3; and m is 0, 1 or 2.

[0018] In still further embodiments of the above, the intermediate haloalkane is 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and / or 1,1,1,2,3-pentafluoropropane (HFC-245eb).

[0019] The second haloolefin can, in certain embodiments, be any compound of formula (III): (CX n Y 3-n )(CR 1 a R 2 b ) Z CX=CH m+1 X 1-m (III) wherein each X is independently Cl, F, I or Br, provided that at least two X are F; each Y is independently H, Cl, F, I or Br; each R 1 R2 is independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; each R2 is independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; n is 1, 2 or 3; a and b are each 0, 1 or 2, provided that a+b=2; m is 0 or 1; and z is 0, 1, 2 or 3.

[0020] In further embodiments of the above, the second haloolefin comprises or consists of a compound of formula (IIIA): (CX n Y 3-n )CX=CH m+1 X 1-m (IIIA) wherein each X is independently Cl, F, I or Br, provided that at least two X are F; each Y is independently H, Cl, F, I or Br; n is 1, 2 or 3; and m is 0 or 1.

[0021] In still further embodiments of the above, the second haloolefin is 2,3,3,3-tetrafluoropropene (1234yf) and / or 1,1,1,2,3-pentafluoropropene (HFO-1225ye).

[0022] In the embodiment where the second halogenated olefin is HFO-1225ye and / or HFO-1234yf, for example, the aforementioned reaction can be carried out in a single facility with four unit operations. More specifically, it is known to produce HFC-236ea and HFC-245eb by hydrogenation of HFP with hydrogen. Similar to HFC-236ea, HFC-245eb can then be dehydrofluorinated to produce the desired product. In particular, HFC-236ea can be dehydrofluorinated to produce HFO-1225ye, and HFC-245eb can be dehydrofluorinated to produce HFO-1234yf. Therefore, a single set of four unit operations can be used to simultaneously produce HFO-1225ye and HFO-1234yf: hydrogenating the raw materials, separating the desired intermediates, dehydrofluorinating the intermediates to produce the desired products, followed by another separation to separate the desired products. For example, in one system, HFP and H2 react in a hydrogenation reactor to form an intermediate product stream containing HFC-236ea and / or HFC-245eb. The relative concentrations of HFC-236ea and HFC-245eb depend on the reaction conditions in the hydrogenation reactor, such as the relative concentrations of the pressure, temperature and reactants in the reactor. If the desired final product is HFO-1225ye, the processing conditions preferably facilitate the generation of HFC-236ea. In other words, the hydrogenation reactor is operated to produce an intermediate product stream rich in HFC-236ea, and then HFC-236ea is separated from the intermediate process stream and sent to a dehydrofluorination reactor to form a final product stream containing HFO-1225ye. This HFO-1225ye is subsequently separated from the final product stream and recovered as a purified product. If the desired final product is HFO-1234yf, the processing conditions preferably facilitate the generation of HFC-245eb. In other words, the hydrogenation reactor is operated to produce an intermediate product stream rich in HFC-245eb. This can be achieved by operating the hydrogenation reactor under conditions that are favorable for converting HFP to HFC-236ea and then converting HFC-236ea to HFC-245eb. HFC-245eb is then separated from the intermediate product stream and sent to a dehydrofluorination reactor to form a final product stream containing HFO-1234yf. This HFO-1234yf is then separated from the final product stream and recovered as a purified product.

[0023] In addition, when HFO-1234yf is the desired product, HFO-1225ye can be introduced into the hydrogenation reactor at a certain point and then converted into HFC-245eb. This HFO-1225ye source can be a separate feed stream and / or a recycle stream (i.e., recycled HFO-1225ye derived from HFC-236ea as described above). HFC-245eb is then separated from the intermediate product stream and sent to a dehydrofluorination reactor to form a final product stream containing HFO-1234yf. This HFO-1234yf is subsequently separated from the final product stream and recovered as a purified product.

[0024] For any of the foregoing, the dehydrofluorination step (e.g., 245eb→1234yf or 236ea→1225ye) is carried out in the presence of at least one dehydrohalogenating agent, such as, but not limited to, potassium hydroxide (KOH), sodium hydroxide (NaOH), calcium hydroxide (Ca(OH)2), lithium hydroxide (LiOH), magnesium hydroxide (Mg(OH)2), calcium oxide (CaO), or a combination thereof. The amount of reagent used or the molar ratio of reagent to organic varies with the specific parameters present in each embodiment as discussed above or elsewhere herein. In certain embodiments, the molar ratio of dehydrohalogenating agent to organic feed (e.g., HFC-245eb and / or HFC-236ea) is less than 1 to 3, preferably 1-1.5.

[0025] Dehydrohalogenation can be carried out in any suitable reaction vessel or reactor. In certain non-limiting embodiments, the reactor comprises one or a series of continuously stirred tank reactors (CSTRs), wherein organic matter (e.g., HFC-236ea and / or HFC-245eb) and dehydrohalogenation agent are continuously fed into the reactor. The waste dehydrohalogenation agent stream can be taken out from the reaction product stream and purified in a continuous or intermittent manner.

[0026] In certain embodiments, the waste dehydrohalogenation agent stream further includes one or more dissolved organics, such as, but not limited to, HFC-236ea and / or HFC-245eb. The waste dehydrohalogenation agent can be purified from such organics using one or more known separation methods. Such methods include, but are not limited to, distillation and / or phase separation. The resulting dehydrohalogenation agent can then be optionally concentrated and recycled back to the dehydrohalogenation reaction independently or with one or more organics as provided herein.

[0027] In further embodiments, the product stream also includes a salt byproduct of the dehydrohalogenation reaction. The salt byproduct can be separated from the product stream using known techniques and converted back to the dehydrohalogenation agent using known methods. It can then be recycled back to the dehydrohalogenation reaction independently or together with one or more organics provided herein.

[0028] As a non-limiting example, one such salt byproduct may be potassium fluoride (KF) formed when potassium hydroxide is used as a dehydrohalogenating agent. KF may be converted to KOH by treatment with Ca(OH)2 (calcium hydroxide) according to the following reaction: 2KF + Ca(OH)2 → 2KOH + CaF2 The resulting KOH can be optionally concentrated and recycled back to the dehydrohalogenation reaction either independently or with one or more organics as provided herein.

[0029] Other embodiments and advantages of the present invention will be apparent to those skilled in the art based on the disclosure provided herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is a process flow diagram showing the production of fluorinated olefins according to one embodiment of the present invention.

[0031] Figure 2 is a process flow diagram showing a hydrogenation unit operation according to one embodiment of the present invention.

[0032] Figure 3 is a process flow diagram showing a hydrogenation unit operation according to another embodiment of the present invention.

[0033] Figure 4 is a process flow diagram showing the operation of the first separation unit according to one embodiment of the present invention and Figure 4A is a process flow diagram showing additional separation unit operations according to one embodiment of the present invention.

[0034] Figure 5 is a process flow diagram showing the operation of the first separation unit according to another embodiment of the present invention.

[0035] Figure 6 is a process flow diagram showing a dehydrofluorination unit operation according to one embodiment of the present invention.

[0036] Figure 7 is a process flow diagram showing a dehydrofluorination unit operation according to another embodiment of the present invention. DETAILED DESCRIPTION

[0037] The present invention relates, at least in part, to methods for improving the cost efficiency of a dehydrohalogenation production process for fluorinated olefins by recovering and recycling spent dehydrohalogenation agents. On the one hand, the present invention relates to dehydrohalogenation of fluorinated alkanes (e.g., pentafluoropropane and / or hexafluoropropane) in the presence of a dehydrohalogenation agent to produce fluorinated olefins (e.g., tetrafluoropropene and / or pentafluoropropene). Removing spent dehydrohalogenation agents from the reactor reduces design and operating costs, and recycling of spent and / or regenerated dehydrohalogenation agents achieves improved efficiency. In certain embodiments, the dehydrohalogenation agent may include, but is not limited to, potassium hydroxide (KOH), sodium hydroxide (NaOH), calcium hydroxide (Ca(OH)2), lithium hydroxide (LiOH), magnesium hydroxide (Mg(OH)2), calcium oxide (CaO), or a combination thereof. In further embodiments, the dehydrohalogenation agent is potassium hydroxide (KOH).

[0038] In certain embodiments, the fluorinated olefins of the present invention include one or more C3 to C6 fluorinated olefins, preferably compounds having the formula: X 1 CF z R 3-z Where X 1 is a C2, C3, C4 or C5 unsaturated, substituted or unsubstituted hydrocarbon group, each R is independently Cl, F, Br, I or H, and z is 1 to 3. Highly preferred among such compounds are propylene and butene having 3 to 5 fluorine substituents, with tetrafluoropropylene (HFO-1234) and pentafluoropropylene (HFO-1225) being particularly preferred.

[0039] In one embodiment, the method for making fluorinated olefins of the present invention comprises reacting a fluorinated olefin raw material having a halogen substitution degree of N+1 and having substantially the same number of carbon atoms as one or more fluorinated olefins having a halogen substitution degree of N to be synthesized. The fluorinated olefin raw material preferably, but not limited to, has a fluorine substitution degree of N+1 and is exposed to effective reaction conditions that effectively produce a reaction product containing one or more fluorinated alkanes having the same number of carbon atoms as the final olefin. This olefin conversion step includes reactions that are sometimes referred to herein as a reduction or hydrogenation step for convenience but not necessarily by way of limitation. The resulting fluorinated alkane is subsequently converted into a fluorinated olefin having a fluorine substitution degree of N. This alkane conversion step includes reactions that are sometimes referred to herein as a dehydrohalogenation reaction for convenience but not necessarily by way of limitation or more particularly as a dehydrofluorination or dehydrochlorination reaction in certain embodiments.

[0040] Based on the above, in one aspect of the present invention, a method for producing a fluorinated olefin comprises the following steps: (a) hydrogenating a compound of formula (I) under effective conditions: (CX n Y3-n )(CR 1 a R 2 b ) z CX=CH m X 2-m (I) The effective conditions are such as to be effective to form at least one fluorinated alkane of formula (II): (CX n Y 3-n )(CR 1 a R 2 b ) z CHX m+1 X 2-m (II) in: each X is independently Cl, F, I or Br, provided that at least two X are F; Each Y is independently H, Cl, F, I or Br; Each R 1 are independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; Each R2 is independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; n is 1, 2, or 3; a and b are each 0, 1 or 2, provided that a+b=2; m is 0, 1 or 2; and z is 0, 1, 2 or 3; and (b) dehydrohalogenating a compound of formula (II) under conditions effective to produce a fluorinated olefin having a lower degree of fluorine substitution than the compound of formula (I), preferably to produce a compound of formula (III): (CX n Y 3-n )(CR 1 a R 2 b ) Z CX=CH m+1 X 1-m (III) wherein each n has the same value as in formula (I), and m is 0 or 1.

[0041] In a further non-limiting embodiment, the reactant of formula (I) may include a three-carbon olefin of formula (IA) wherein z is 0, i.e. CX n Y 3-n CX=CH m X2-m (IA) To produce a three-carbon alkane of formula (IIA): (CX n Y 3-n )CHXCH m+1 X 2-m (IIA) wherein X, Y, n and m are as shown above, and then the compound is dehydrohalogenated to form a compound of formula (IIIA): (CX n Y 3-n )CX=CH m+1 X 1-m (IIIA) wherein n has the same value as in formula (IA), and m is 0 or 1.

[0042] In yet further embodiments, the invention provides a saturated terminal carbon of a compound of formula (I) or (IA) completely substituted with fluorine (e.g., n on the saturated terminal carbon is 3 and each X on that carbon is F). In such embodiments, the compound of formula (I) or (IA) is preferably a fluoropropene having 3 to 6 fluorine substituents and possibly other halogen substituents, including, for example, hexafluoropropene (i.e., Z is 0, n is 3, m is 0 and all X are F) or pentafluoropropene (i.e., Z is 0, n is 3, m is 1 and all X are F). The resulting compound of formula (II) or (IIA) is selected from one or more of the following fluorinated alkanes: pentafluoropropane (HFC-245) and hexafluoropropane (HFC-236), including all isomers of each of these, but preferably 1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and combinations of these. In certain preferred embodiments, the fluorinated alkane produced by this conversion step has a degree of fluorine substitution of N+1.

[0043] In any of the above reactions, the step of converting the olefin to the alkane is carried out under conditions effective to provide a conversion of at least about 40%, more preferably at least about 55%, and even more preferably at least about 70% to the compound of formula (I). In certain preferred embodiments, the conversion is at least about 90%, and even more preferably about 99%. In certain preferred embodiments, the conversion of the compound of formula (I) or (IA) to produce the compound of formula (II) is carried out under conditions effective to provide a selectivity of at least about 60%, more preferably at least about 80%, even more preferably at least about 90%, and even more preferably about 100% to the compound of formula (II) or (IIA).

[0044] In any of the above reactions, the step of converting the alkane to a fluorinated olefin having a degree of fluorination of N is carried out under conditions effective to provide a conversion of at least about 40%, more preferably at least about 55%, and even more preferably at least about 70% to the compound of formula (II). In certain preferred embodiments, the conversion is at least about 90%, and even more preferably about 95%. In certain preferred embodiments, the conversion of the compound of formula (II) to produce the compound of formula (III) is carried out under conditions effective to provide a selectivity of at least about 60%, more preferably at least about 80%, even more preferably at least about 90%, and even more preferably about 98% to the compound of formula (III).

[0045] Hydrogenation step Although the hydrogenation or reduction steps are expected to be carried out in batch operations, the hydrogenation reaction is preferably carried out as a substantially continuous operation. Although the hydrogenation reaction is expected to be carried out in a single reactor, the reaction step may include any combination of two or more reactors or reaction stages or reactor designs in parallel and / or in series. In addition, the reaction step is expected to include one or more feed preheating steps or stages depending on the details of each application.

[0046] Although the reaction may in certain embodiments comprise a liquid phase reaction, in certain embodiments the hydrogenation reaction is contemplated to comprise at least one vapor phase reaction stage.

[0047] In such Figure 2 In one embodiment of the invention shown in , the hydrogenation step comprises a reaction step A, which is associated with at least a first flow path or feed stream 1A, at least a second flow path or feed stream 1B, and at least a third flow path or feed stream 2, each of which can be operated independently. In such an embodiment, preferably, the first flow path or feed stream 1A contains HFP and preferably substantially all of the HFP is fed to reaction step A, and the second flow path or feed stream 1B contains HFO-1225ye and preferably substantially all of the HFO-1225ye is fed to reaction step A (it is recognized that feed stream 1B has essentially zero flow in many embodiments, and in other embodiments such feed stream 1B can actually be a recycle stream from a subsequent operation in the process). Feed stream 2 contains a hydrogenating agent or a reducing agent for reaction step A, preferably H2. Flow path or stream 4 is a path that enables the introduction of a recycle stream into the reaction step. In some embodiments, the actual flow rate of recycle stream 4 is zero, but in preferred embodiments, the recycle stream comprises a relatively low temperature stream comprising a portion of reaction product stream 3A after cooling and / or separation, and when present, the contents of recycle stream 4 are preferably relatively rich in HFC-236ea, HFC-245eb, or a combination of these.

[0048] In such Figure 3In another preferred embodiment of the present invention shown in, the hydrogenation step comprises at least the first reaction step A1 and the second reaction step A2. In one embodiment, the first reaction step A1 may comprise one or more reaction stages in parallel or in series or in a series-parallel combination, which is associated with at least the first flow path or feed stream 1A and at least the second flow path or feed stream 2A, and each flow path can be operated independently. In such an embodiment, preferably, the first flow path or feed stream 1A comprises HFP and preferably substantially all HFP is sent to the reaction step A, and the second flow path or feed stream 2A comprises a hydrogenating agent for the reaction step A, preferably H2. Flow path or stream 4A is a path that enables the introduction of a recycle stream into the reaction step. In some embodiments, the actual flow rate of the recycle stream 4A is substantially zero, but in a preferred embodiment, the recycle stream comprises a relatively low temperature stream, which comprises a portion of the reaction product stream 3A after cooling and / or separation, and when present, the contents of the recycle stream 4 are preferably relatively rich in HFC-236ea, HFC-245eb or a combination of these.

[0049] For the reaction stage of converting HFP in a hydrogenation reactor in step A1, a trickle bed reactor is preferably used in certain embodiments. The reaction is expected to proceed as follows: CF3CF=CF2+H2→CF3CHFCF2H(HFC-236ea). The main side reactions of this process produce HFC-245eb and HF. It is believed that 245eb is formed from 236ea by hydrodefluorination and / or by dehydrofluorination followed by reduction: HFC-236ea+H2→HFC-245eb+HF.

[0050] The second reaction step A2 may include one or more reaction stages in parallel or in series or in a combination of series and parallel, and the step is associated with at least the first flow path or feed stream 1B and at least the second flow path or feed stream 2B, and each flow path can be operated independently. In such an embodiment, the first flow path or feed stream 1B, when present, preferably includes HFO-1225ye and preferably substantially all HFO-1225ye is sent to reaction step A. The second flow path or feed stream 2B includes a hydrogenating agent for reaction step A2, preferably H2. Flow path or stream 4B is a path that enables the introduction of a recycle stream into the reaction step. In some embodiments, the actual flow rate of recycle stream 4B is zero, but in a preferred embodiment, the recycle stream includes a relatively low temperature stream, which includes a portion of the reaction product stream 3A and / or 3B after cooling and separation, and when present, the content of recycle stream 4B is preferably relatively rich in HFC-236ea, HFC-245eb or a combination of these. Flow path or stream 10 is a pathway that enables the introduction of a second recycle stream into the reaction step, which in a preferred embodiment comprises at least a portion of reaction product stream 6 processed into a stream comprising a stream relatively rich in HFO-1225ye.

[0051] For the reaction stage of converting HFO-1225ye in a hydrogenation reactor in step A2, a trickle bed reactor is preferably used in certain embodiments. The reaction is expected to proceed as follows: CF3CF=CFH(liq)+H2(gas)→CF3CHFCFH2(HFC-245eb-gas) The main side effects are expected to be: HFC-245eb+H2→CF3CHFCH3(HFC-254)+HF.

[0052] The hydrogenation reaction conditions in the reaction are preferably controlled to achieve the desired conversion and / or selectivity according to the present invention. The term "reaction conditions" used herein is intended to include the singular and refers to the control of any one or more processing parameters, including the possible use or non-use of reaction vessels or stages, which can be modified by the operator of the reaction to produce feed conversion and / or selectivity according to the teachings contained herein. For example, but not limited to, the conversion of the feed can be controlled or adjusted by controlling or adjusting any one or more of the following: reaction temperature, flow rate of reactants, presence of diluents, amount of catalyst present in the reactor, shape and size of the reactor, reaction pressure and any combination of these and other process parameters available and known to those skilled in the art based on the disclosure contained herein. The size and shape and other characteristics of the reaction vessel itself can be widely varied within the scope of the present invention, and the containers associated with each stage are expected to be different or the same as the containers associated with the upstream and downstream reaction stages. In addition, all reaction stages are expected to be carried out in a single container, provided that the means and mechanisms necessary for controlling the conversion are provided. For example, in certain embodiments it is desirable to use a single tubular reactor for each reaction stage, providing conversion control by judicious selection of the amount and / or distribution of catalyst throughout the tubular reactor. In such cases, the conversion in different sections of the same tubular reactor can be further controlled by controlling the amount of heat removed from or added to different sections of the tubular reactor.

[0053] Those skilled in the art can easily select the type of catalyst (or catalysts) for the hydrogenation step of the present invention based on the teachings contained herein. For example, in certain embodiments, preferably at least one, but preferably all reaction stages utilize a palladium catalyst, preferably 1% carbon-supported palladium, alone or in combination with other catalysts. In this regard, one or more hydrogenation catalysts disclosed in U.S. Pat. No. 5,679,875, which is incorporated herein by reference, can be used in one or more reaction stages according to the present invention. In certain preferred embodiments, the catalyst preferably comprises palladium supported on carbon, such as a carbon net.

[0054] Therefore, certain embodiments of the process of the present invention include contacting a fluorinated olefin according to Formula I and a hydrogenating agent such as H2 with a first amount of a catalyst in at least a first reaction stage to produce a reaction stream comprising one or more hydrofluorocarbons, unreacted fluorinated olefins and hydrogen. In certain preferred embodiments, a preferred separation step as described below is performed after the hydrogenation step. Although it is expected that a wide variety of hydrogenation reaction temperatures may be used depending on relevant factors (such as the catalyst used and the most desired reaction product), the reaction temperature of the hydrogenation step is generally preferably about 50°C to about 150°C, preferably about 75°C to about 115°C, and more preferably about 90°C to about 100°C.

[0055] In general, it is also expected that a wide variety of reaction pressures may be used depending on relevant factors such as the specific catalyst used and the most desired reaction product. The reaction pressure may be, for example, about 100 psig to about 300 psig, preferably about 150 psig to about 250 psig, and more preferably about 200 psig.

[0056] Applicants have discovered, without being bound by any particular theory, that the use of a cooled recycle stream 4, 4A or 4B in the hydrogenation reaction enables the feed to act as a means of removing heat from the hydrogenation reaction. Since the reduction or hydrogenation reaction of the present invention is generally exothermic and generally significantly exothermic, the use of such a recycle material has the effect, in a preferred embodiment, of maintaining the reactor temperature below the temperature that would exist if all other process conditions were held the same but no recycle was used.

[0057] The amount of hydrogen used is expected to vary widely. In a preferred embodiment, hydrogen is fed to the reaction step as a gas at a H2:olefin feed ratio of about 1:1 to about 2:1, more preferably about 1:1 to about 1.5:1, and more preferably about 1.3:1.

[0058] Hydrogenation effluent separation In certain preferred embodiments, the present invention further comprises the step of cooling at least a portion of the reactor product stream (3, 3A, 3B) to remove at least a portion of the heat of reaction. In many preferred embodiments, this cooling step is included as a combination of Figure 4 , 5 6 and 7. The ratio of the cooled recycled reaction product to the fresh feed is preferably about 12:1, and the temperature of the recycled stream is preferably about 50° C. to about 100° C., more preferably about 70° C. In addition, to aid in the removal of the heat of reaction, it is preferred in certain embodiments to introduce the fresh feed and / or recycled feed into the reaction in the liquid phase and allow the heat of reaction to vaporize the liquid feed and / or reaction product and to remove the reaction product in the vapor phase.

[0059] Now refer to Figure 4 , the reaction product streams 3A and 3B are sent to a separation step B, which is Figure 4In an embodiment, a cooling step B1 is included, which produces one or more cooled reaction product streams 3AB, which are in turn sent to one or more separation stages B2. It is expected that a person skilled in the art will be able to conceive of many means and mechanisms for achieving such cooling based on the teachings contained herein without undue experimentation, and all such means and mechanisms are within the scope of the present invention. The preferred separation step B2 preferably includes at least a first separation step, which produces a first stream 4 relatively rich in unreacted hydrogen, fluorinated alkanes such as HFC-236ea and / or HFC-245eb, or a combination of these, which can be recycled to the reaction step A with or without further processing. A second stream 5 relatively rich in fluorinated alkanes such as HFC-236ea and / or HFC-245eb is also produced by the separation step B2.

[0060] exist Figure 4A In a preferred embodiment shown in , the separation step comprises, in addition to a cooling step B1 and a separation step B2, the separation step B2 produces at least a first cooling stream 4A and a crude product stream 100, the first cooling stream 4A containing a portion of the reaction products and preferably recycled to the reaction step A), while the crude product stream 100 is sent to a further separation step B3, wherein a significant portion of the excess hydrogen in the stream 100 is purged and sent to disposal or further processing in stream 4B. Stream 101 from separation step B3 is subsequently sent to a further separation step B4, wherein unwanted by-products are removed in stream 4C and one or more product streams 5A and 5B are produced. In a preferred embodiment, stream 5A is relatively rich in the first fluorinated alkane, preferably HFC-236ea, and the second stream 5B is rich in the second fluorinated alkane, preferably HFC-245eb.

[0061] Refer to now Figure 5 In another embodiment described, the reaction product streams 3A and 3B are each sent to separate separation steps, including separate cooling steps B1 and B1', which each produce one or more cooled reaction product streams 3A' and 3B', which are in turn sent to separate separation stages B2 and B2' to produce a first stream 5A relatively rich in the first fluorinated alkane product (when the feed stream 3A is rich in HFP, such as HFC-236ea) and a second reaction product stream 5B relatively rich in the second fluorinated alkane product (when the feed stream 3B is rich in HFO-1225ye, such as HFC-245eb). It is also possible to remove the above-mentioned reaction product streams from each step B2 and B2'. Figure 4 The described material stream 4 (not shown). In addition, Figure 4A The specific embodiments shown and described in the Figure 5 One or both of the separation steps B and B' shown in are used in combination.

[0062] Dehydrohalogenation The dehydrofluorination step can be carried out in the liquid phase in the presence of a dehydrohalogenating agent (eg, caustic solution) or in the vapor phase in the presence of a dehydrofluorination catalyst. It is contemplated that the reaction can be carried out batchwise, continuously, or in a combination of processes.

[0063] In one embodiment, the conversion step comprises contacting HFC-245eb and / or HFC-236ea with a dehydrohalogenating agent such as KOH, NaOH, Ca(OH)2, LiOH, Mg(OH)2, CaO, and combinations thereof to form a fluorinated olefin. For example, if KOH is used, by way of example and not necessarily limitation, the reaction can be described by the following reaction equations (1) and (2): CF3-CHF-CHF2 + KOH → CF3CF=CHF + KF + H2O (1) CF3-CHF-CH2F + KOH → CF3CF=CH2 + KF + H2O (2).

[0064] The dehydrohalogenation agent can be provided as a caustic aqueous solution containing about 2% to about 100%, more preferably about 10% to about 50%, and even more preferably about 10% to about 30% by weight of the dehydrohalogenation agent. In a further embodiment, the caustic solution, preferably the dehydrohalogenation agent solution, is brought to a temperature of about 20°C to about 100°C, more preferably about 20°C to about 90°C, and most preferably about 20°C to about 70°C. The reaction pressure in such an embodiment can vary depending on the specific processing parameters of each application. In certain embodiments, the reaction pressure is atmospheric pressure, superatmospheric pressure, or vacuum. When used, the vacuum pressure is about 5 torr to about 760 torr in certain embodiments.

[0065] The amount of dehydrohalogenation agent (or reagent) used or the reagent / organic molar ratio is expected to vary depending on the specific parameters used in each embodiment. In certain embodiments, the molar ratio of dehydrohalogenation agent to organic feed (e.g., HFC-245eb and / or HFC-236ea) is less than 1 to 3, preferably 1-1.5. In further embodiments, the contact time expressed as the ratio of reagent volume (ml) to total feed flow rate (ml / sec) is from about 0.1 seconds to about 1000 seconds, preferably from about 2 seconds to about 120 seconds.

[0066] Any suitable container or reactor can be used to realize dehydrohalogenation reaction.Such container or reactor should be made of corrosion-resistant materials, such as stainless steel, nickel and its alloy, including Hastelloy, Inconel, Incoloy and Monel.In certain embodiments, one or a series of continuous stirred tank reactors (CSTR) are used to carry out this reaction.In this type of reactor, organic feed (such as HFC-236ea and / or HFC-245eb) and dehydrohalogenation agent are continuously fed into reactor and the resulting product stream formed is fed into a condenser or distillation column for separating 1225ye and / or 1234yf and unreacted 236ea and / or 245eb and other by-products of the reaction.

[0067] In certain embodiments, the waste dehydrohalogenation agent is removed from the product stream periodically or continuously and recycled back to the reactor for reuse. As shown above, the applicant has found that in the continuous processing process, the reaction proceeds until the organic reactant (e.g., HFC-236ea and / or HFC-245eb) or the dehydrohalogenation agent is exhausted. This increases production costs because the reactor must be disassembled after the reaction is completed to remove salts and / or salt solutions. However, by recycling the dehydrohalogenation agent and the by-product salt, this cost can be reduced and the system can be made more effective.

[0068] The spent dehydrohalogenating agent and byproduct salts (e.g., metal fluoride salts) can be removed from the reactor through the product stream continuously or intermittently using one or more known separation techniques. To this end, any known compound separation technique, such as, but not limited to, distillation, phase separation, etc., can be used to separate the spent dehydrohalogenating agent. In certain embodiments, the removal of the spent dehydrohalogenating agent is particularly beneficial for component separation because it allows the organic matter to be easily separated from the dehydrohalogenating agent. This in turn achieves lower costs associated with the design and operation of complex and highly specialized separation equipment.

[0069] The product stream containing the waste dehydrohalogenation agent usually carries some dissolved organic matter (for example HFC-236ea and / or HFC-245eb). By stopping the agitator and then removing the waste dehydrohalogenation agent during the time of stopping stirring, the separation of the dehydrohalogenation agent and such organic matter can be promoted. The waste dehydrohalogenation agent and the dissolved organic matter are sent to a container, where one or more of the above-mentioned separation techniques are used to realize the additional separation of the dehydrohalogenation agent and the organic matter. In a non-limiting embodiment, for example, KOH is separated by distillation, i.e., by heating the organic matter at a boiling point slightly higher than 236ea and / or 245eb to fractionate the organic matter from the waste KOH. Alternatively, a phase separator can be used to separate the two phases. The KOH separated product without organic matter can be immediately recycled to the reactor or can be concentrated and the concentrated solution is sent back to the reactor.

[0070] The byproduct salt can also be separated and converted back to a dehydrohalogenating agent using known methods. When KOH is used as a dehydrohalogenating agent, for example, KF is formed as a byproduct salt. Such salts can be converted back to KOH and recycled back to the dehydrohalogenating reaction. For example, Ca(OH)2 can be used for KF conversion according to the following reaction. 2KF+Ca(OH)2→2KOH+CaF2.

[0071] While the KOH is separated and recycled back to the reactor, CaF2 is precipitated from the above reaction. The recycling of the spent dehydrohalogenating agent achieves better reagent usage efficiency. In addition, the use of byproduct salt recycling reduces the amount of dehydrohalogenating agent used, reducing reagent costs and costs associated with the disposal of salts and / or the purchase of new raw materials.

[0072] In one embodiment of the present invention and with reference to Figure 6 , the dehydrohalogenation step comprises a reaction step C, which is associated with at least a first flow path or feed stream 5A, at least a second flow path or feed stream 5B and at least a third flow path or feed stream 8, each flow path being independently operable. In such an embodiment, preferably. The first flow path or feed stream 5A comprises HFO-236ea and preferably substantially all HFO-236ea is fed to reaction step C, and the second flow path or feed stream 5B comprises HFC-245eb and preferably substantially all HFO-245eb is fed to reaction step C (it is to be recognized that feed stream 5B has substantially zero flow in many embodiments). Flow path or stream 8 is a path that enables a recycle stream to be introduced into the reaction step. In some embodiments, the actual flow of recycle stream 8 is zero, but in a preferred embodiment, the recycle stream comprises a relatively low temperature stream, which comprises a portion of the reaction product stream 6A after cooling and / or separation. When present, the contents of recycle stream 8 may include unreacted organics (eg, HFC-236ea, HFC-245eb) and spent dehydrohalogenation agent. Each may be purified or recovered as provided herein and recycled.

[0073] exist Figure 7In another preferred embodiment of the present invention shown in , the dehydrohalogenation step comprises at least a first reaction step C1 and a second reaction step C2. The first reaction step C1 may comprise one or more reaction stages in parallel or in series or in a combination of series and parallel, which are associated with at least a first flow path or feed stream 5A and at least a second flow path or feed stream 8A, and each flow path can be operated independently. The second reaction step C2 may comprise one or more reaction stages in parallel or in series or in a combination of series and parallel, which are associated with at least a first flow path or feed stream 5B and at least a second flow path or feed stream 8B, and each flow path can be operated independently. In such an embodiment, preferably, the first flow path or feed stream 5A contains HFO-236ea and preferably substantially all HFO-236ea is fed to reaction step C, and the second flow path or feed stream 5B contains HFO-245eb when present and preferably substantially all HFO-245eb is fed to reaction step C. Flow paths or streams 8A and 8B are flow paths that allow for the introduction of a recycle stream comprising at least a portion of unreacted feed or recycled dehydrohalogenating agent as defined herein. In some embodiments, the actual flow of recycle streams 8A and 8B is substantially zero, but in preferred embodiments, the recycle stream comprises a relatively low temperature stream comprising a portion of the reaction product streams 6A and 6B after cooling and separation.

[0074] The reaction conditions in the reaction are preferably controlled to achieve the desired conversion and / or selectivity according to the present invention. The term "reaction conditions" used herein is intended to include the singular and refers to the control of any one or more processing parameters, including the possible use or non-use of reaction vessels or stages, which can be modified by the operator of the reaction to produce feed conversion and / or selectivity according to the teachings contained herein. For example, but not limited to, the conversion of the feed can be controlled or adjusted by controlling or adjusting any one or more of the following: reaction temperature, flow rate of reactants, presence of diluent, amount of catalyst present in the reactor, shape and size of the reactor, reaction pressure and any combination of these and other process parameters available and known to those skilled in the art based on the disclosure contained herein. The size and shape and other characteristics of the reaction vessel itself can be widely varied within the scope of the present invention, and the container associated with each stage is expected to be different or the same as the container associated with the upstream and downstream reaction stages. In addition, all reaction stages are expected to be carried out in a single container, provided that the means and mechanisms necessary for controlling the conversion are provided. For example, in certain embodiments, it is desired to use a single tubular reactor for each reaction stage, and conversion control is provided by carefully selecting the amount and / or distribution of catalysts at various locations of the tubular reactor. In such cases, the conversion in different sections of the same tubular reactor can be further controlled by controlling the amount of heat removed from or added to the different sections of the tubular reactor.

[0075] The resulting product may be separated from the product stream and purified accordingly using one or more methods known in the art. Example

[0076] The following examples are provided in order to illustrate the invention but not to limit its scope.

[0077] Embodiment 1: 245eb is converted into 1234yf using CSTR (continuous stirred tank reactor). The reactor is designed and operated so that the end of the dip tube is in the middle of the KOH phase. After startup, organic matter and KOH are continuously fed. The organic matter output (overhead distillate portion) is continuously taken out. In a typical cycle, organic matter and KOH flow into and take out the overhead distillate for 30 minutes. The flow rates are 5 and 12 ml / min respectively. The mixture is stirred during this period. Then the agitator is stopped for 10 minutes while still continuing to feed. While the agitator is turned off, after 10 minutes, the valve for the waste KOH to flow out is opened. 500 to 550 grams are taken out every 40 minutes.

[0078] The experiment was run for 7 hours. The temperature was 48°C. The pressure was 45 psig. The GC area % of the organic feed was ~97% 245eb, with the remainder most likely 254. The flow rate converted to a KOH / G-245eb mole ratio of 1 or slightly above 1. The theoretical residence time was 100 minutes.

[0079] The waste KOH and the organic fraction carried out with the waste KOH were collected using a scrubber product collection cylinder (SPCC). The organics were captured in the methylene chloride previously added to the SPCC. The volume of methylene chloride in the SPCC was 15% of the total liquid volume in the SPCC. The products and unreacted organics were collected in a product collection cylinder (PCC) placed in dry ice. Vapor samples were extracted once an hour, while liquid samples were extracted at much longer intervals.

[0080] The total mass balance of organics was 94%. The average conversion was 48%. The selectivity to 1234yf was 73%.

[0081] Embodiment 2: A second experiment was conducted in the same manner as experiment 1, except that the pressure and temperature were 48 psig and 47° C. The experiment lasted 6 hours and the total conversion was 69%. The selectivity to 1234yf was 75%.

[0082] Embodiment 3: 807 ml of organics were loaded in the reactor. Analysis of the feed by GC showed an area % of 236ea of ​​97.70%. There was no 1234yf in this feed, and the percentage of 1225ye was 0.03. After loading the organics in the reactor, 1641 ml of 25% KOH was added. The molar ratio of KOH to 236ea was therefore 1.23.

[0083] The flow rates of 236ea and KOH were 2 and 4 ml / min. The pressure was 35-45 psig. The reactor temperature was 42-45°C.

[0084] Spent KOH was periodically removed from the reactor (it was fed continuously like the organics; the overhead product was removed continuously, i.e., semi-continuous operation). In this semi-continuous mode, KOH and organics flowed into the stirred reactor for 50 minutes. The agitator was then stopped for 10 minutes while the reactants were still flowing. Thereafter, 290-300 grams of spent KOH were removed. The agitator and timer were then started for 50 minutes.

[0085] Spent KOH was collected in a scrubber product collection cylinder (SPCC). The SPCC was pre-filled with dichloromethane (target was to have 15-20 wt% dichloromethane in the final spent KOH-dichloromethane solution). Analysis of the dichloromethane layer showed ~70GC area % was 236ea. There was a small amount of 1225ye (~2%) and the rest was unidentified heavies. To confirm that all organics were extracted with dichloromethane, some KOH was added to some MeCl2 (i.e. 1:1). GC analysis showed negligible amounts of organics.

[0086] The total mass balance was 88.67%. The residence time was 200 minutes. The conversion was -50%. The selectivity to 1225ye was 63%. The reaction was run for a total of 97 hours.

[0087] This application may include the following technical solutions.

[0088] Scheme 1. A method for producing at least one fluorinated olefin, comprising: a. hydrogenating a feed stream comprising at least one olefin according to formula (I): (CX n Y 3-n )(CR 1 a R 2 b ) z CX=CH m X 2-m (I) It is carried out by contacting the feedstock with a reducing agent to produce an intermediate product stream comprising at least one alkane according to formula (II): (CXn Y 3-n )(CR 1 a R 2 b ) z CHX m+1 X 2-m (II) in: each X is independently Cl, F, I or Br, provided that at least two X are F; Each Y is independently H, Cl, F, I or Br; Each R 1 are independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; Each R2 is independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; n is 1, 2, or 3; a and b are each 0, 1 or 2, provided that a+b=2; m is 0, 1 or 2; and z is 0, 1, 2, or 3; b. Optionally, separating the intermediate product stream into a plurality of intermediate product streams, the plurality of intermediate product streams comprising two or more streams selected from a first stream rich in at least a first alkane according to Formula II, a second stream rich in at least a second alkane according to Formula II, and an alkane recycle stream; c. dehydrofluorinating at least a portion of the intermediate process stream from step (a) or the plurality of intermediate process streams from step (b) in the presence of a dehydrohalogenating agent to produce an olefin product stream comprising 1,1,1,2,3-pentafluoropropene and at least one additional olefin having a lower degree of fluorination than the compound of formula (I); and d. withdrawing a product reaction stream comprising spent dehydrohalogenating agent from the dehydrofluorination product stream; and e. Recovering the spent dehydrohalogenation agent.

[0089] Scheme 2. The method of Scheme 1, wherein the additional olefin is a compound according to formula (III): (CX n Y 3-n )(CR 1 a R 2 b ) Z CX=CH m+1 X 1-m (III) Where X, Y, R 1 , R 2, n, a and b are each the same value as in formula (I) and m is 0 or 1.

[0090] Scenario 3. The process of Scenario 1, wherein the feed stream comprises hexafluoropropylene and the additional olefin is 1,1,1,2-tetrafluoropropylene.

[0091] Scheme 4. The method of Scheme 1, wherein the dehydrohalogenating agent is selected from KOH, NaOH, Ca(OH)2, LiOH, Mg(OH)2, CaO and combinations thereof.

[0092] Scheme 5. A method for producing 1,1,1,2-tetrafluoropropene, comprising: a. hydrogenating a feed stream comprising hexafluoropropylene to produce an intermediate stream comprising 1,1,1,2,3-pentafluoropropane or 1,1,1,2,3,3-hexafluoropropane by contacting the feed stream with a reducing agent in a hydrogenation reactor; b. dehydrofluorinating the 1,1,1,2,3-pentafluoropropane or the 1,1,1,2,3,3-hexafluoropropane in the presence of a dehydrohalogenating agent in a dehydrofluorination reactor to produce a product stream comprising 1,1,1,2-tetrafluoropropene or 1,1,1,2,3-pentafluoropropene; c. removing a second product stream comprising spent dehydrohalogenating agent from the product stream; d. Recovering the spent dehydrohalogenation agent; and e. Optionally, concentrating the purified dehydrohalogenating agent and recycling it back to the dehydrohalogenating reaction.

[0093] Option 6. The process of Option 5, wherein the second product stream further comprises dissolved organic matter selected from 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and / or 1,1,1,2,3-pentafluoropropane (HFC-245eb).

[0094] Scheme 7. The method of Scheme 5, wherein the reaction stream further comprises a byproduct salt of a dehydrohalogenating agent.

[0095] Scheme 8. The method of Scheme 7 further comprises converting the by-product salt into the dehydrohalogenating agent.

[0096] Scheme 9. The process of Scheme 7, wherein the dehydrohalogenating agent is KOH and the byproduct salt is KF.

[0097] Scheme 10. A method for producing a fluorinated olefin, comprising: (a) dehydrohalogenating 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) or 1,1,1,2,3-pentafluoropropane (HFC-245eb) in the presence of KOH to produce 2,3,3,3-tetrafluoropropane (HFO-1234yf) or 1,2,3,3,3-pentafluoropropene (HFO-1225ye); (b) withdrawing a reaction stream comprising spent KOH, dissolved organics, and optionally KF; (c) recovering waste KOH; (d) optionally converting KF into KOH.

[0098] Scheme 11. The method of Scheme 10, further comprising optionally concentrating the converted KOH and recycling it back to the dehydrohalogenation reaction.

Claims

1. A method for producing at least one fluorinated olefin, comprising: a. hydrogenating a feed stream comprising at least one olefin according to formula (I): (CX n Y 3-n )(CR 1 a R 2 b ) z CX=CH m X 2-m (I) It is carried out by contacting the feedstock with a reducing agent to produce an intermediate product stream comprising at least one alkane according to formula (II): (CX n Y 3-n )(CR 1 a R 2 b ) z CHX m+1 X 2-m (II) in: each X is independently Cl, F, I or Br, provided that at least two X are F; Each Y is independently H, Cl, F, I or Br; Each R 1 are independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; Each R2 is independently H, Cl, F, I, Br or unsubstituted or halogen-substituted methyl or ethyl; n is 1, 2, or 3; a and b are each 0, 1 or 2, provided that a+b=2; m is 0, 1 or 2; and z is 0, 1, 2, or 3; b. Optionally, separating the intermediate product stream into a plurality of intermediate product streams, the plurality of intermediate product streams comprising two or more streams selected from a first stream rich in at least a first alkane according to Formula II, a second stream rich in at least a second alkane according to Formula II, and an alkane recycle stream; c. dehydrofluorinating at least a portion of the intermediate process stream from step (a) or the plurality of intermediate process streams from step (b) in the presence of a dehydrohalogenating agent to produce an olefin product stream comprising 1,1,1,2,3-pentafluoropropene and at least one additional olefin having a lower degree of fluorination than the compound of formula (I); and d. withdrawing a product reaction stream comprising spent dehydrohalogenating agent from the dehydrofluorination product stream; and e. Recovering the spent dehydrohalogenation agent.

2. The process of claim 1, wherein the additional olefin is a compound according to formula (III): (CX n Y 3-n )(CR 1 a R 2 b ) Z CX=CH m+1 X 1-m (III) Where X, Y, R 1 , R 2 , n, a and b are each the same value as in formula (I) and m is 0 or 1.

3. A method for producing 1,1,1,2-tetrafluoropropene, comprising: a. hydrogenating a feed stream comprising hexafluoropropylene to produce an intermediate stream comprising 1,1,1,2,3-pentafluoropropane or 1,1,1,2,3,3-hexafluoropropane by contacting the feed stream with a reducing agent in a hydrogenation reactor; b. dehydrofluorinating the 1,1,1,2,3-pentafluoropropane or the 1,1,1,2,3,3-hexafluoropropane in the presence of a dehydrohalogenating agent in a dehydrofluorination reactor to produce a product stream comprising 1,1,1,2-tetrafluoropropene or 1,1,1,2,3-pentafluoropropene; c. removing a second product stream comprising spent dehydrohalogenating agent from the product stream; d. Recovering the spent dehydrohalogenation agent; and e. Optionally, concentrating the purified dehydrohalogenating agent and recycling it back to the dehydrohalogenating reaction.

4. A method for producing a fluorinated olefin, comprising: (a) dehydrohalogenating 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) or 1,1,1,2,3-pentafluoropropane (HFC-245eb) in the presence of KOH to produce 2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,2,3,3,3-pentafluoropropene (HFO-1225ye); (b) withdrawing a reaction stream comprising spent KOH, dissolved organics, and optionally KF; (c) recovering waste KOH; (d) optionally converting KF into KOH.

5. Use of 1,1,1,2,3-pentafluoropropene (HFO-1225ye), 2,3,3,3-tetrafluoropropene (HFO-1234yf) or a mixture of HFO-1225ye and HFO-1234yf as a disinfectant.

6. A method for recycling KOH in a dehydrohalogenation reaction, the method comprising: Using KOH as a dehydrohalogenation agent in a dehydrohalogenation reaction to obtain KF; reacting the obtained KF with Ca(OH)2 to produce KOH; and The resulting KOH is recycled to the dehydrohalogenation reaction.

7. A process for preparing fluorinated olefins by dehydrohalogenating fluorinated alkanes in the presence of a dehydrohalogenating agent, wherein the dehydrohalogenation is carried out in a reactor comprising a series of continuously stirred tank reactors (CSTRs).

8. A dehydrohalogenation catalyst selected from the group consisting of fluorinated chromium oxide catalysts, aluminum fluoride catalysts, iron fluoride catalysts, a mixture of magnesium fluoride and aluminum fluoride catalysts, nickel-based catalysts, carbon-based catalysts, and combinations thereof.

9. A facility with four unit operations, the unit operations being Hydrogenation of raw materials, Isolation of the desired intermediates, dehydrofluorination of the desired intermediate to produce the desired product, Separation is performed to isolate the desired product.

10. The dehydrofluorination reactor is one or a series of continuous stirred tank reactors.

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