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 U.S. Patent Application No. 202111058499.8, filed October 7, 2011, entitled "Integrated Method for Manufacturing Fluorinated Olefins". Application No. 202111058499.8 is a divisional application of U.S. Patent Application No. 201711048814.2, filed October 7, 2011, entitled "Integrated Method for Manufacturing Fluorinated Olefins". Application No. 201711048814.2 is a divisional application of U.S. Patent Application No. 201180059852.2, filed October 7, 2011, entitled "Integrated Method for Manufacturing Fluorinated Olefins". This application relates to and claims priority to U.S. Provisional Application No. 61 / 392,242, filed October 12, 2010, the contents of which are hereby incorporated herein by reference.

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

[0003] This invention relates to methods for manufacturing haloolefins, particularly, but not limited to, 2,3,3,3-tetrafluoropropane (HFO-1234yf) and / or 1,2,3,3,3-pentafluoropropene (HFO-1225ye). Background Technology

[0004] Chlorinated 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. These chlorinated compounds have been proven 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, there is a global effort to develop new compounds that are more environmentally friendly and simultaneously effective or more efficient in terms of performance.

[0005] The applicant has recognized that 1,1,1,2,3-pentafluoropropylene (HFO-1225ye) and 1,1,1,2-tetrafluoropropylene (HFO-1234yf) can each be used for one or more of the aforementioned uses. Therefore, compositions containing either or both of these fluorinated olefins belong to materials developed for such uses.

[0006] Methods for producing HFO-1234yf and HFO-1225ye are known. In one instance, 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 produce 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 subsequently be dehydrofluorinated to produce HFO-1234yf.

[0007] U.S. Patent Application Publication 2009 / 0234165 (the contents of which are incorporated herein by reference) further proposes that HFO-1225ye and HFO-1234yf can be manufactured in a single facility. Most notably, it is recognized that the hydrogenation of HFP can produce HFC-236ea and HFC-245eb, and that 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 the other. Catalysts that can be used for such reactions are taught to include metal catalysts, more preferably one or more transition metal-based catalysts (including transition metal halide catalysts in some preferred embodiments), such as supported or bulk FeCl3, chromium fluoride, 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 producing HFO-1225ye and HFO-1234yf are described in at least U.S. Patent No. 7,560,602, which are assigned to the assignee of this invention and are hereby incorporated herein by reference. This patent discloses similar dehydrohalogenation methods for producing 2,3,3,3-tetrafluoropropylene (1234yf) and 1,1,1,2,3-pentafluoropropane (HFC-236ea), respectively, via catalytic dehydrofluorination of 1,1,1,2,3-pentafluoropropane (245eb) and 1,1,1,2,3,3-hexafluoropropane (HFC-236ea). Preferred dehydrohalogenation catalysts include chromium oxide fluoride 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 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 some embodiments, the dehydrohalogenating agent includes KOH, and optional reagents include LiOH, Mg(OH)₂, and NaOH.

[0010] The applicant has recognized that in continuous processing using such a dehalogenating agent (also referred to as "reagent"), the reaction proceeds until the organic reactants or the dehalogenating agent are exhausted. After the reaction is complete, the reactor must be dismantled to remove the salt and / or salt solution. This results in high operating costs and reduced productivity. Therefore, a more efficient method is needed to remove waste reagents and recycle unused or regenerated reagents and / or unused organic matter in continuous processes.

[0011] The applicant believes that this invention addresses the aforementioned needs. Summary of the Invention

[0012] This invention relates at least in part to a method for improving the cost efficiency of a process for producing fluorinated olefins by recycling and reusing waste reagents. In one aspect, the invention relates to the dehydrohalogenation of fluorinated alkanes (e.g., pentafluoropropane and / or hexafluoropropane) in the presence of a dehydrohalogenating agent to produce fluorinated olefins (e.g., tetrafluoropropylene and / or pentafluoropropylene). Such dehydrohalogenating 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. Removing the waste dehydrohalogenating agent from the reactor facilitates the separation of organic matter from the dehydrohalogenating agent. This, in turn, leads to lower costs associated with the design and operation of complex and highly specialized separation equipment. Recycling of the waste dehydrohalogenating agent results in even higher efficiency. Similarly, increased productivity is observed if metal fluoride salts are also separated from the product stream, converted back to the original form of the dehydrohalogenating agent, and recycled to the reaction.

[0013] On one hand, the present invention relates to a method or process for manufacturing fluorinated olefins, comprising: (a) hydrogenating a first haloalkene to produce a haloalkane; (b) optionally separating the haloalkane 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 recycling stream; (c) dehydrohalogenating the haloalkane in (a) or (b) in the presence of a dehydrohalogenating agent to produce a second haloalkene; (d) removing the reaction stream containing waste dehydrohalogenating agent and optionally a metal fluoride salt byproduct; and (e) recovering, purifying, and / or regenerating the waste dehydrohalogenating agent. The first haloalkene may include compounds of formula (I): (CX n Y 3-n (CR) 1 a R 2 b ) z CX = CH m X 2-m (I) 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 Each R2 is independently H, Cl, F, I, Br or unsubstituted or halogenated methyl or ethyl; each R2 is independently H, Cl, F, I, Br or unsubstituted or halogenated 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 a further embodiment described above, the first haloolefin includes or is composed of a compound of formula (IA): CX n Y 3-n CX = CH m X 2-m (IA) 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 a further embodiment described above, the first haloalkane is hexafluoropropylene (HFP).

[0016] In some embodiments, the first haloalkane in this reaction method can be any compound of formula (II): (CX n Y 3-n (CR) 1 a R 2 b )z CHXCH m+1 X 2-m (II) 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 Each R2 is independently H, Cl, F, I, Br or unsubstituted or halogenated methyl or ethyl; each R2 is independently H, Cl, F, I, Br or unsubstituted or halogenated 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 a further embodiment described above, the haloalkane is a compound of formula (IIA): (CX n Y 3-n CHXCH m+1 X 2-m (IIA) 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 a further embodiment described 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] In some embodiments, the second haloalkene can 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) 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 Each R2 is independently H, Cl, F, I, Br or unsubstituted or halogenated methyl or ethyl; each R2 is independently H, Cl, F, I, Br or unsubstituted or halogenated 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 a further embodiment described above, the second haloolefin includes or is composed of a (IIIA) compound: (CX n Y 3-n )CX=CH m+1 X 1-m (IIIA) 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 a further embodiment described above, the second halogenated olefin is 2,3,3,3-tetrafluoropropylene (1234yf) and / or 1,1,1,2,3-pentafluoropropylene (HFO-1225ye).

[0022] In embodiments where the second haloolefin 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, hydrogenation of HFP with hydrogen is known to produce HFC-236ea and HFC-245eb. Similar to HFC-236ea, HFC-245eb can subsequently 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. Thus, HFO-1225ye and HFO-1234yf can be produced simultaneously using a single set of four unit operations: hydrogenation of the feedstock, separation of the desired intermediate, dehydrofluorination of the intermediate to produce the desired product, followed by another separation to further separate the desired product. 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 pressure, temperature, and relative concentrations of the reactants. If the desired final product is HFO-1225ye, the processing conditions preferably promote the formation of HFC-236ea. That is, 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 fed into a defluorination reactor to form a final product stream containing HFO-1225ye. This HFO-1225ye is then separated from the final product stream and recovered as a purified product. If the desired final product is HFO-1234yf, the processing conditions preferably promote the formation of HFC-245eb. That is, 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 favorable to the conversion of HFP to HFC-236ea and subsequently to HFC-245eb. HFC-245eb is then separated from the intermediate product stream and fed into a defluorination 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] Furthermore, 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 fed into the defluorination reactor to form a final product stream containing HFO-1234yf. Subsequently, this HFO-1234yf is separated from the final product stream and recovered as a purified product.

[0024] In any of the foregoing cases, the defluorination step (e.g., 245eb→1234yf or 236ea→1225ye) is carried out in the presence of at least one dehalogenating 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 combinations thereof. The amount of reagent used or the molar ratio of reagent to organic matter varies with the specific parameters present in the embodiments discussed above or elsewhere herein. In some embodiments, the molar ratio of the dehalogenating agent to the organic feed (e.g., HFC-245eb and / or HFC-236ea) is less than 1 to 3, preferably 1 to 1.5.

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

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

[0027] In a further embodiment, the product stream also includes salt byproducts from the dehydrohalogenation reaction. The salt byproducts can be separated from the product stream using known techniques and converted back to the dehydrohalogenating agent using known methods. They can then be recycled back to the dehydrohalogenation reaction, either independently or together with one or more organic compounds provided herein.

[0028] As a non-limiting example, one such salt byproduct could be potassium fluoride (KF), formed when potassium hydroxide is used as a dehydrohalogenating agent. KF can 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 together with one or more organic compounds as provided herein.

[0029] Other embodiments and advantages of the present invention will be readily apparent to those skilled in the art based on the disclosure provided herein. Attached Figure Description

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

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

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

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

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

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

[0036] Figure 7 This is a process flow diagram showing the operation of the defluorination unit according to another embodiment of the present invention. Detailed Implementation

[0037] This invention relates at least in part to a method for improving the cost efficiency of dehydrohalogenation production processes of fluorinated olefins by recovering and recycling waste dehydrohalogenating agents. 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 olefins (e.g., tetrafluoropropylene and / or pentafluoropropylene). Removing waste dehydrohalogenating agents from the reactor reduces design and operating costs, and the recycling of waste and / or regenerated dehydrohalogenating agents achieves improved efficiency. In some embodiments, the dehydrohalogenating 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 combinations thereof. In a further embodiment, the dehydrohalogenating agent is potassium hydroxide (KOH).

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

[0039] In one embodiment, the method of producing fluorinated olefins according to the present invention comprises reacting a fluorinated olefin feedstock having a halogen substitution degree of N+1, having substantially the same number of carbon atoms as one or more fluorinated olefins to be synthesized having a halogen substitution degree of N. The fluorinated olefin feedstock preferably, but not limited to, has a fluorine substitution degree of N+1 and is exposed to effective reaction conditions that enable efficient production of reaction products containing one or more fluorinated alkanes having the same number of carbon atoms as the final olefin. This olefin conversion step includes reactions sometimes referred to herein as reduction or hydrogenation steps for convenience but not necessarily as limiting the terminology. The resulting fluorinated alkane is then converted into a fluorinated olefin with a fluorine substitution degree of N. This alkane conversion step includes reactions sometimes referred to herein as dehydrohalogenation reactions for convenience but not necessarily as limiting the terminology, or more specifically as dehydrofluorination or dehydrochlorination reactions in some embodiments.

[0040] Based on the above, in one aspect of the present invention, a method for manufacturing fluorinated olefins includes the following steps: (a) Hydrogenation of compound (I) under effective conditions: (CX n Y3-n (CR) 1 a R 2 b ) z CX = CH m X 2-m (I) These effective conditions enable the efficient formation of at least one fluorinated alkane of formula (II): (CX n Y 3-n (CR) 1 a R 2 b ) z CHXCH 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 can be independently H, Cl, F, I, or Br; Each R 1 It is independently H, Cl, F, I, Br, or an unsubstituted or halogen-substituted methyl or ethyl group; Each R2 is independently H, Cl, F, I, Br, or an unsubstituted or halogen-substituted methyl or ethyl group; n is 1, 2, or 3; a and b are 0, 1 or 2 respectively, and the condition is a + b = 2; m is 0, 1, or 2; and z is 0, 1, 2, or 3; and (b) Dehydrohalogenating compound (II) under conditions that effectively produce a fluorinated olefin with a fluorine substitution degree lower than that of compound (I), preferably producing compound (III): (CX n Y 3-n (CR) 1 a R 2 b ) Z CX = CH m+1 X 1-m (III) Each n has the same value as in equation (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 the following formula (IIA): (CX n Y 3-n CHXCH m+1 X 2-m (IIA) Where X, Y, n, and m are as shown above, the compound is then dehydrohalogenated to form a compound of formula (IIIA): (CX n Y 3-n )CX=CH m+1 X 1-m (IIIA) Where n has the same value as in equation (IA), and m is 0 or 1.

[0042] In a further embodiment, the invention provides a saturated terminal carbon of a compound of formula (I) or (IA) that is completely fluorinated (e.g., n is 3 on the saturated terminal carbon and each X on that carbon is F). In such an embodiment, the compound of formula (I) or (IA) is preferably a fluoropropylene having 3 to 6 fluorinated substituents and possibly other halogenated substituents, including, for example, hexafluoropropylene (i.e., Z is 0, n is 3, m is 0 and all X are F) or pentafluoropropylene (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 of these respective isomers, but preferably 1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), and combinations thereof. In some preferred embodiments, the fluorinated alkanes produced by this conversion step have a fluorine substitution degree of N+1.

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

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

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

[0046] Although the reaction may include a liquid phase reaction in some embodiments, the hydrogenation reaction is expected to include at least one gas phase reaction stage in some embodiments.

[0047] In such Figure 2 In one embodiment of the invention shown, the hydrogenation step comprises a reaction step A 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 flow path being operable independently. In such an embodiment, preferably, the first flow path or feed stream 1A contains HFP and preferably feeds substantially all of the HFP into reaction step A, and the second flow path or feed stream 1B contains HFO-1225ye and preferably feeds substantially all of the HFO-1225ye into reaction step A (it should be recognized that feed stream 1B has substantially zero flow in many embodiments, and in other embodiments such feed stream 1B can actually be a recirculated stream from subsequent operations in the method). Feed stream 2 contains a hydrogenating agent or reducing agent for reaction step A, preferably H2. Flow path or feed stream 4 is a path that enables the introduction of a recirculated stream into the reaction step. In some embodiments, the actual flow rate of the recirculation stream 4 is zero, but in a preferred embodiment, the recirculation stream comprises a relatively low-temperature feed stream containing a portion of the cooled and / or separated reaction product stream 3A. When present, the contents of the recirculation stream 4 are preferably relatively rich in HFC-236ea, HFC-245eb, or a combination thereof.

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

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

[0050] The second reaction step A2 may comprise one or more reaction stages in parallel, series, or a combination of series and parallel, associated with at least a first flow path or feed stream 1B and at least a second flow path or feed stream 2B, each flow path being operable independently. In such an embodiment, the first flow path or feed stream 1B, when present, preferably contains HFO-1225ye and preferably feeds substantially all of the HFO-1225ye into reaction step A. The second flow path or feed stream 2B contains a hydrogenating agent, preferably H2, for reaction step A2. Flow path or feed stream 4B is a path that allows a recirculation stream to be introduced into the reaction step. In some embodiments, the actual flow rate of the recirculation stream 4B is zero, but in a preferred embodiment, the recirculation stream comprises a relatively low-temperature stream containing a portion of the cooled and separated reaction product streams 3A and / or 3B, and when present, the contents of the recirculation stream 4B are preferably relatively rich in HFC-236ea, HFC-245eb, or combinations thereof. The flow path or feed stream 10 is a path that enables the introduction of a second recirculated flow into the reaction step, which in a preferred embodiment includes at least a portion of the reaction product stream 6 that has been processed to contain a relatively rich HFO-1225ye.

[0051] For the reaction stage A2, in which HFO-1225ye is converted in the hydrogenation reactor, a trickle bed reactor is preferred in some 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] Preferably, the hydrogenation reaction conditions in this reaction are controlled to achieve the desired conversion and / or selectivity according to the invention. The term "reaction conditions" as 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 absence of reaction vessels or stages, which can be modified by the operator of the reaction to produce the feed conversion and / or selectivity according to the teachings contained herein. For example, but not limited to, feed conversion can be controlled or adjusted by controlling or regulating any one or more of the following: reaction temperature, reactant flow rate, presence of diluent, amount of catalyst present in the reactor, reactor shape and size, reaction pressure, and any combination thereof, as well as other process parameters available and known to those skilled in the art based on the disclosure contained herein. The size, shape, and other characteristics of the reaction vessels can themselves vary widely within the scope of the invention, and the vessels associated with each stage are expected to be different from or the same as those associated with upstream and downstream reaction stages. Furthermore, all reaction stages are expected to be carried out within a single vessel, provided that the means and mechanisms necessary for controlling the conversion are provided. For example, in some implementations it is desirable to use a single tubular reactor for each reaction stage, providing conversion control through careful selection of the amount and / or distribution of catalyst throughout the tubular reactor. In such cases, conversion in different sections of the same tubular reactor can be further controlled by controlling the heat removed from or added to different sections of the tubular reactor.

[0053] Those skilled in the art will readily select the type of catalyst (or multiple catalysts) for the hydrogenation steps of the present invention based on the teachings contained herein. For example, in some embodiments, at least one, but preferably all reaction stages utilize a palladium catalyst, either alone or in combination with other catalysts, preferably 1% carbon-supported palladium. In this regard, one or more hydrogenation catalysts disclosed in U.S. Patent 5,679,875, which is incorporated herein by reference, can be used in one or more reaction stages according to the present invention. In some preferred embodiments, the catalyst preferably comprises palladium supported on carbon, such as a carbon mesh.

[0054] Therefore, certain embodiments of the method 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 catalyst in at least a first reaction stage to produce a reaction feed stream comprising one or more hydrofluorocarbons, unreacted fluorinated olefins, and hydrogen. In some preferred embodiments, a preferred separation step as described below is performed after the hydrogenation step. Although a wide variety of hydrogenation reaction temperatures are expected to be used depending on relevant factors such as the catalyst used and the most desired reaction products, the reaction temperature of the hydrogenation step is generally preferably from about 50°C to about 150°C, more preferably from about 75°C to about 115°C, and even more preferably from about 90°C to about 100°C.

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

[0056] The applicant has discovered that, without being bound by any particular theory, the use of a cooled recirculated stream 4, 4A, or 4B in a hydrogenation reaction allows the feed to act as a means of removing heat from the hydrogenation reaction. Since the reduction or hydrogenation reactions of the present invention are typically exothermic and often significantly so, the use of such recycled material in a preferred embodiment has the effect of maintaining the reactor temperature below the temperature that would exist assuming all other process conditions remain the same without the use of recirculation.

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

[0058] Hydrogenation reaction effluent separation In some preferred embodiments, the invention further includes the step of cooling at least a portion of the reactor product streams (3, 3A, 3B) to remove at least a portion of the heat of reaction. In many preferred embodiments, this cooling step is included as part of the following combination. Figure 4 , 5 This is part of a preferred aspect of separation step B described in section 6. The ratio of cooled recycled reaction product to fresh feed is preferably about 12:1, and the temperature of the recycled stream is preferably from about 50°C to about 100°C, more preferably about 70°C. Furthermore, to facilitate the removal of heat of reaction, in some embodiments, it is preferable to introduce the fresh feed and / or recycled feed into the reaction in the liquid phase and allow the heat of reaction to evaporate the liquid feed and / or reaction product, and to remove the reaction product in the gas phase.

[0059] Now refer to Figure 4 The reaction product streams 3A and 3B are sent to separation step B, where... Figure 4The implementation includes a cooling step B1, which produces one or more cooled reaction product streams 3AB, which are then fed into one or more separation stages B2. It is expected that those skilled in the art will conceive of numerous means and mechanisms for achieving such cooling based on the teachings contained herein, without extensive experimentation, and all such means and mechanisms are within the scope of the 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 combinations thereof, which may be recycled to reaction step A with or without further processing. Separation step B2 also produces a second stream 5 relatively rich in fluorinated alkanes such as HFC-236ea and / or HFC-245eb.

[0060] exist Figure 4A In a preferred embodiment shown, in addition to the cooling step B1 and the separation step B2, the separation step includes: separation step B2 producing at least a first cooled feed stream 4A and a crude product stream 100, the first cooled feed stream 4A containing a portion of the reaction products and preferably recycled to reaction step A), while the crude product stream 100 is sent to a further separation step B3, in which a large portion of the excess hydrogen in the stream is removed and sent to disposal or further processed in feed stream 4B. The feed stream 101 from separation step B3 is then sent to a further separation step B4, in which unwanted byproducts are removed in feed stream 4C and one or more product streams 5A and 5B are produced. In a preferred embodiment, feed stream 5A is relatively rich in a first fluorinated alkane, preferably HFC-236ea, and the second feed stream 5B is rich in a second fluorinated alkane, preferably HFC-245eb.

[0061] In the present reference Figure 5 In another described embodiment, reaction product streams 3A and 3B are each fed to separate separation steps, including separate cooling steps B1 and B1', each producing one or more cooled reaction product streams 3A' and 3B', which are then fed into separate separation stages B2 and B2' to produce a first stream 5A relatively rich in the first fluorinated alkane product (e.g., HFC-236ea when feed stream 3A is rich in HFP) and a second reaction product stream 5B relatively rich in the second fluorinated alkane product (e.g., HFC-245eb when feed stream 3A is rich in HFO-1225ye). The above-described combination can also be removed from each of steps B2 and B2'. Figure 4 The described material flow 4 (not shown). Furthermore, Figure 4A The specific implementation schemes shown and described herein can also be applied to [other applications]. Figure 5 The separation steps B and B' shown are used in combination or together.

[0062] Dehydrohalogenation The dehydrofluorination step can be carried out in the liquid phase in the presence of a dehalogenating agent (e.g., a caustic alkali solution) or in the gas phase in the presence of a dehydrofluorination catalyst. The reaction is expected to proceed in a batch, continuous, or combined manner.

[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, or combinations thereof, to form a fluorinated olefin. For example, if KOH is used, this reaction can be described, by way of example but not necessarily by way of limitation, 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 dehydrohalogenating agent can be provided as an aqueous caustic alkali 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 dehydrohalogenating agent. In a further embodiment, the caustic alkali solution, preferably the dehydrohalogenating 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 embodiments can vary depending on the specific processing parameters for each application. In some embodiments, the reaction pressure is atmospheric pressure, extra-atmospheric pressure, or vacuum. When used, the vacuum pressure in some embodiments is about 5 Torr to about 760 Torr.

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

[0066] The dehydrohalogenation reaction can be carried out using any suitable vessel or reactor. Such a vessel or reactor should be constructed of corrosion-resistant materials such as stainless steel, nickel, and their alloys, including Hastelloy, Inconel, Incoloy, and Monel. In some embodiments, this reaction is carried out using one or a series of continuous stirred tank reactors (CSTRs). In this type of reactor, an organic feed (e.g., HFC-236ea and / or HFC-245eb) and the dehydrohalogenation agent are continuously fed into the reactor, and the resulting product stream is fed into a condenser or distillation column for separating 1225ye and / or 1234yf from unreacted 236ea and / or 245eb, as well as other byproducts of the reaction.

[0067] In some embodiments, spent dehalogenating agent is periodically or continuously removed from the product stream and recycled back to the reactor for reuse. As shown above, the applicant has found that in continuous processing, the reaction proceeds until the organic reactants (e.g., HFC-236ea and / or HFC-245eb) or the dehalogenating agent is exhausted. This increases production costs because the reactor must be dismantled after the reaction to remove the salt and / or salt solution. However, by recycling the dehalogenating agent and the byproduct salt, these costs can be reduced and the system made more efficient.

[0068] Waste dehalogenating agent and byproduct salts (e.g., metal fluoride salts) can be continuously or intermittently removed from the reactor via the product stream using one or more known separation techniques. For this purpose, any known compound separation technique can be used, such as, but not limited to, distillation, phase separation, etc., for the separation of waste dehalogenating agent. In some embodiments, the removal of waste dehalogenating agent is particularly advantageous for component separation because it facilitates the separation of organic matter from the dehalogenating agent. This, in turn, achieves lower costs associated with the design and operation of complex and highly specialized separation equipment.

[0069] Product streams containing spent dehalogenating agents typically carry some dissolved organic matter (e.g., HFC-236ea and / or HFC-245eb). Separation of the dehalogenating agent and such organic matter can be facilitated by stopping the agitator and then removing the spent dehalogenating agent during the agitation-stopped period. The spent dehalogenating agent and dissolved organic matter are fed into a vessel where additional separation of the dehalogenating agent and organic matter is achieved using one or more of the separation techniques described above. In a non-limiting embodiment, KOH is separated, for example, by distillation, i.e., by heating the organic matter at a boiling point slightly above 236ea and / or 245eb, thereby fractionating the organic matter from the spent KOH. Alternatively, a phase separator can be used to separate the two phases. The organic-free KOH separator can be immediately recycled to the reactor or can be concentrated and the concentrated solution returned to the reactor.

[0070] The byproduct salt can also be separated and converted back to the dehydrohalogenating agent using known methods. When KOH is used as the dehydrohalogenating agent, for example, KF is formed as a byproduct salt. Such a salt 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 KOH is separated and recycled back to the reactor, CaF2 precipitates from the above reaction. Recycling the spent dehalogenating agent achieves better reagent utilization efficiency. Furthermore, the recycling of byproduct salts reduces the amount of dehalogenating agent used, lowering reagent costs and costs associated with salt disposal and / or the purchase of new raw materials.

[0072] In one embodiment of the invention and with reference to Figure 6 The dehydrohalogenation step comprises 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 operable independently. In such an embodiment, preferably, the first flow path or feed stream 5A contains HFO-236ea and preferably feeds substantially all of HFO-236ea into reaction step C, and the second flow path or feed stream 5B contains HFC-245eb and preferably feeds substantially all of HFO-245eb into reaction step C (it should be recognized that feed stream 5B has substantially zero flow in many embodiments). Flow path or feed stream 8 is the path that enables the introduction of a recirculation stream into the reaction step. In some embodiments, the actual flow rate of recirculation stream 8 is zero, but in a preferred embodiment, the recirculation stream comprises a relatively low-temperature stream containing a portion of the cooled and / or separated reaction product stream 6A. When present, the contents of recycle stream 8 may include unreacted organic matter (e.g., HFC-236ea, HFC-245eb) and spent dehalogenating agents. Each may be purified or recovered and recycled as provided herein.

[0073] exist Figure 7In another preferred embodiment of the invention shown, 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, series, or a combination of series and parallel, associated with at least a first flow path or feed stream 5A and at least a second flow path or feed stream 8A, each flow path being operable independently. The second reaction step C2 may comprise one or more reaction stages in parallel, series, or a combination of series and parallel, associated with at least a first flow path or feed stream 5B and at least a second flow path or feed stream 8B, each flow path being operable independently. In such an embodiment, preferably, the first flow path or feed stream 5A comprises HFO-236ea and preferably substantially all of HFO-236ea is fed into reaction step C, and the second flow path or feed stream 5B, when present, comprises HFO-245eb and preferably substantially all of HFO-245eb is fed into reaction step C. Flow paths or feed streams 8A and 8B are flow paths that enable the introduction of a recirculation stream containing at least a portion of unreacted feed or recycled dehalogenating agent, as defined herein. In some embodiments, the actual flow rates of recirculation streams 8A and 8B are essentially zero, but in a preferred embodiment, the recirculation stream comprises a relatively low-temperature feed stream containing a portion of the cooled and separated reaction product streams 6A and 6B.

[0074] The reaction conditions in the reaction are preferably controlled to achieve the desired conversion and / or selectivity according to the invention. The term "reaction conditions" as 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 absence of reaction vessels or stages, which can be modified by the operator of the reaction to produce the feed conversion and / or selectivity according to the teachings contained herein. For example, but not limited to, feed conversion can be controlled or adjusted by controlling or regulating any one or more of the following: reaction temperature, reactant flow rate, presence of diluent, amount of catalyst present in the reactor, reactor shape and size, reaction pressure, and any combination thereof, as well as other process parameters available and known to those skilled in the art based on the disclosure contained herein. The size, shape, and other characteristics of the reaction vessels can vary widely within the scope of the invention, and the vessels associated with each stage are expected to be different from or the same as those associated with upstream and downstream reaction stages. Furthermore, all reaction stages are expected to be carried out in a single vessel, provided that the means and mechanisms necessary to control the conversion are provided. For example, in some embodiments, it is desirable to use a single-tube reactor for each reaction stage, providing conversion control through careful selection of the amount and / or distribution of catalyst throughout the tube reactor. In such cases, the conversion in different sections of the same tubular reactor can be further controlled by controlling the heat removed from or added to different sections of the tubular reactor.

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

[0076] The following embodiments are provided to illustrate the invention and not to limit its scope.

[0077] Example 1: 245eb was converted to 1234yf using a CSTR (Continuous Stirred Tank Reactor). The reactor was designed and operated such that the end of the dip tube was in the middle of the KOH phase. After startup, organic matter and KOH were continuously fed in. The organic matter output (the overhead distillate portion) was continuously withdrawn. In a typical cycle, the organic matter and KOH flowed in and the overhead distillate was withdrawn for 30 minutes at flow rates of 5 and 12 mL / min, respectively. The mixture was stirred during this period. The stirrer was then stopped for 10 minutes while the feed continued. After 10 minutes, the valve allowing waste KOH to drain was opened simultaneously with the stirrer shutdown. 500 to 550 g were withdrawn every 40 minutes.

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

[0079] Waste KOH and the organic fraction carried over with it were collected using a scrubber product collection cartridge (SPCC). The organic fraction was trapped in dichloromethane previously added to the SPCC. The volume of dichloromethane in the SPCC was 15% of the total liquid volume in the SPCC. Products and unreacted organic fractions were collected in a product collection cartridge (PCC) placed on dry ice. Vapor samples were extracted hourly, while liquid samples were extracted at much longer intervals.

[0080] The total mass balance of organic matter was 94%. The average conversion rate was 48%. The selectivity for 1234yf was 73%.

[0081] Example 2: The 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 for 6 hours, with an overall conversion rate of 69%. The selectivity for 1234yf was 75%.

[0082] Example 3: 807 mL of organic matter was loaded into the reactor. GC analysis of the feed showed that the area percentage of 236ea was 97.70%. There was no 1234yf in this feed, while the percentage of 1225ye was 0.03%. After loading the organic matter into the reactor, 1641 mL of 25% KOH was added. Therefore, the molar ratio of KOH to 236ea was 1.23.

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

[0084] Waste KOH is periodically removed from the reactor (it is fed in continuously like organic matter; the top product is continuously removed, i.e., semi-continuous operation). In this semi-continuous mode, KOH and organic matter flow into the stirred reactor for 50 minutes. Then, the stirrer is stopped for 10 minutes while the reactants are still flowing in. After that, 290-300 grams of waste KOH are removed. Then, the stirrer and timer are started and run for 50 minutes.

[0085] Waste KOH was collected in a product collection cartridge (SPCC) of the scrubber. The SPCC was pre-filled with dichloromethane (the target was 15-20% by weight of dichloromethane in the final waste KOH-dichloromethane solution). Analysis of the dichloromethane layer showed an area of ​​236 ea at approximately 70% GC. A small amount of 1225 ea (approximately 2%) was present, with the remainder being unidentified heavy matter. To confirm that all organic matter had been extracted with dichloromethane, a portion of KOH was added to a portion of MeCl2 (i.e., 1:1). GC analysis showed that the amount of organic matter was negligible.

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

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

[0088] Option 1. A method for producing at least one fluorinated olefin, comprising: a. Hydrogenating a feed stream containing 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 raw material with a reducing agent to produce an intermediate product stream containing at least one alkane according to formula (II): (CX n Y3-n (CR) 1 a R 2 b ) z CHXCH 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 can be independently H, Cl, F, I, or Br; Each R 1 It is independently H, Cl, F, I, Br, or an unsubstituted or halogen-substituted methyl or ethyl group; Each R2 is independently H, Cl, F, I, Br, or an unsubstituted or halogen-substituted methyl or ethyl group; n is 1, 2, or 3; a and b are 0, 1 or 2 respectively, and the condition is a + b = 2; m is 0, 1, or 2; and z is 0, 1, 2, or 3; b. Optionally, the intermediate product stream is separated 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 a first alkane according to Formula II, a second stream rich in a second alkane according to Formula II, and an alkane recycling 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-pentafluoropropylene and at least one additional olefin with a lower degree of fluorination than the compound of formula (I); and d. Remove the product reaction stream containing the waste dehalogenating agent from the defluorination product stream; and e. Recycle waste dehalogenating agents.

[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 equation (I) and m is 0 or 1.

[0090] Option 3. The method of Option 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] Option 5. A method for producing 1,1,1,2-tetrafluoropropylene, comprising: a. A feed stream containing hexafluoropropylene is hydrogenated by contacting the feed stream with a reducing agent in a hydrogenation reactor to produce an intermediate feed stream containing 1,1,1,2,3-pentafluoropropane or 1,1,1,2,3,3-hexafluoropropane. b. Defluorinating the 1,1,1,2,3-pentafluoropropane or the 1,1,1,2,3,3-hexafluoropropane in a defluorination reactor in the presence of a dehalogenating agent to produce a product stream containing 1,1,1,2-tetrafluoropropene or 1,1,1,2,3-pentafluoropropene. c. Remove a second product stream containing the waste dehalogenating agent from the product stream; d. Recovering waste dehalogenation agents; and e. Optionally, the purified dehydrohalogenating agent is concentrated and recycled back to the dehydrohalogenating reaction.

[0093] Scheme 6. The method of Scheme 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 feed further comprises a byproduct salt of the dehydrohalogenating agent.

[0095] Option 8. The method of Option 7 further includes converting the byproduct salt into the dehydrohalogenating agent.

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

[0097] Option 10. A method for manufacturing fluorinated olefins, 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) Remove the reaction stream containing waste KOH, dissolved organic matter, and optional KF; (c) Recycle waste KOH; (d) Optionally convert KF to KOH.

[0098] Scheme 11. The method of Scheme 10 further includes 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 feedstock containing at least one olefin, said at least one olefin including hexafluoropropylene. It is carried out by contacting the raw material with a reducing agent to produce an intermediate product stream containing at least one alkane, the at least one alkane including 1,1,1,2,3,3-hexafluoropropane and 1,1,1,2,3-pentafluoropropane; b. Optionally, the intermediate product stream is separated 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 1,1,1,2,3,3-hexafluoropropane, a second stream rich in 1,1,1,2,3-pentafluoropropane, and an alkane recycling stream; c. Dehydrofluorinating at least a portion of the intermediate product stream from step (a) or the plurality of intermediate product streams from step (b) in the presence of a dehydrohalogenating agent to produce an olefin product stream comprising 1,1,1,2,3-pentafluoropropylene and at least one additional olefin, wherein the at least one additional olefin comprises 2,3,3,3-tetrafluoropropylene, wherein the dehydrohalogenating agent is KOH. d. Remove the product reaction stream containing waste KOH, dissolved organic matter, and KF from the olefin product stream; e. Recovering waste KOH, wherein recovering waste KOH includes separating waste KOH and KF from dissolved organic matter in the product reaction stream; and f. Recycle the waste KOH recovered from step (e) back to the dehydrohalogenation reaction.

2. The method of claim 1, wherein step (b) is absent.

3. The method of claim 1, wherein step (b) is present.

4. The method of claim 1, wherein the reducing agent comprises H2.

5. The method of any one of claims 1-4, further comprising converting KF to KOH.

6. The method of claim 5, further comprising concentrating the converted KOH and recycling it back to the dehydrohalogenation reaction.

7. The method of claim 1, wherein waste KOH is removed from the defluorination product stream continuously or intermittently during the dehydrohalogenation reaction.

8. A method for producing 2,3,3,3-tetrafluoropropylene, comprising: a. A feed stream containing hexafluoropropylene is hydrogenated by contacting the feed stream with a reducing agent in a hydrogenation reactor to produce an intermediate feed stream containing 1,1,1,2,3-pentafluoropropane or 1,1,1,2,3,3-hexafluoropropane. b. Defluorinating the 1,1,1,2,3-pentafluoropropane or the 1,1,1,2,3,3-hexafluoropropane in a defluorination reactor in the presence of a dehalogenating agent to produce a product stream containing 2,3,3,3-tetrafluoropropene or 1,1,1,2,3-pentafluoropropene, wherein the dehalogenating agent is KOH; c. Remove a second product reaction stream containing waste KOH, dissolved organic matter, and KF from the product stream; d. Recovering waste KOH, wherein recovering waste KOH includes separating waste KOH and KF from dissolved organic matter in the second product reaction stream; and e. Concentrate the purified KOH and recycle it back to the dehydrohalogenation reaction.

9. The method of claim 8, wherein the dissolved organic matter is selected from 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and / or 1,1,1,2,3-pentafluoropropane (HFC-245eb).

10. The method of claim 8, further comprising converting KF to KOH.

11. The method of claim 8, further comprising concentrating the converted KOH and recycling it back to the dehydrohalogenation reaction.

12. The method of claim 8, wherein the reducing agent comprises H2.

13. The method of any one of claims 8-12, wherein waste KOH is removed from the defluorination product stream continuously or intermittently during the dehydrohalogenation reaction.

14. A method for manufacturing fluorinated olefins, 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) Remove the product reaction stream containing waste KOH, KF and dissolved organic matter; (c) Recovering waste KOH, wherein recovering waste KOH includes separating waste KOH and KF from dissolved organic matter in the product reaction stream; (d) Optionally convert KF in waste KOH into KOH; and (e) The waste KOH recovered from step (c) is recycled back to the dehydrohalogenation reaction in step (a).

15. The method of claim 14, further comprising, optionally, concentrating the converted KOH and recycling it back to the dehydrohalogenation reaction.

16. The method of any one of claims 14-15, wherein waste KOH is removed from the defluorination product stream continuously or intermittently during the dehydrohalogenation reaction.

17. The method of claim 14, wherein step (d) is absent.

18. The method of claim 14, wherein step (d) is present.

19. 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.

20. A method for recycling KOH in a dehydrohalogenation reaction, the method comprising: KOH is used as a dehydrohalogenating agent in the dehydrohalogenation reaction to obtain KF; The obtained KF is reacted with Ca(OH)2 to prepare KOH; and The obtained KOH is recycled to the dehydrohalogenation reaction.

21. A method 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 continuous stirred tank reactors (CSTRs).

22. A composition comprising 1,1,1,2,3-pentafluoropropylene (HFO-1225ye) and / or 2,3,3,3-tetrafluoropropylene (HFO-1234yf) for use as a refrigerant, foaming agent, cleaning agent, solvent, heat transfer medium, disinfectant, aerosol propellant, dielectric, fire extinguishing agent and power cycle working fluid.

23. A hydrogenation catalyst selected from metal catalysts, carbon-supported catalysts, antimony-based catalysts, aluminum-based catalysts, palladium-based catalysts, platinum-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts, and combinations thereof.

24. The hydrogenation catalyst of claim 23, wherein the hydrogenation catalyst is a metal catalyst selected from one or more transition metal-based catalysts, transition metal halide catalysts, FeCl3, chromium fluoride, Ni, Ni mesh, NiCl2, CrF3 and mixtures thereof, and the catalyst is supported or bulk.

25. Use of KOH, NaOH, Ca(OH)2, LiOH, Mg(OH)2, CaO or combinations thereof as dehydrohalogenating agents.

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