Compositions containing 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb)

Abstract

To address the issue: because the production of 2,3,3,3-tetrafluoropropene may potentially undergo many undesirable side reactions, there is a need for compositions and methods that enable improved yields, more economical processes, and limited waste generation in the production of 2,3,3,3-tetrafluoropropene and subsequent processes.SOLUTION: The present disclosure provides compositions comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and at least one impurity. Such compositions may be useful for the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf or 1234yf). These compositions may allow for acceptable yields, sufficiently economical processes, and acceptable levels of waste generation in the manufacture of HFO-1234yf.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] This disclosure relates to compositions containing 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and at least one impurity. Such compositions are useful for a variety of purposes, including the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf or 1234yf) and similar compounds. [Background technology]

[0002] Hydrofluoroolefins (HFOs), such as tetrafluoropropene, are known to be effective refrigerants, fire extinguishing agents, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, liquid carriers, buffing agents, displacement desiccants, and power-circulating working fluids. Due to suspected environmental concerns associated with the use of some of these fluids, including their associated relatively high global warming potential, it is desirable to use fluids that have the lowest possible global warming potential (GWP) in addition to also having zero ozone depletion potential (ODP). Accordingly, there is considerable interest in developing environmentally friendly materials for the aforementioned applications.

[0003] HFOs, with their zero ozone depletion and low global warming potential, have been identified as potentially meeting this need. However, the toxicity, boiling points, and other physical properties of such chemicals vary widely between isomers. One HFO with useful properties is 2,3,3,3-tetrafluoropropene (HFO-1234yf or 1234yf).

[0004] HFO-1234yf has been shown to be a low-toxicity, low-global-warming compound, and therefore capable of meeting increasingly stringent refrigerant requirements in mobile air conditioning. Accordingly, compositions containing HFO-1234yf are among the materials being developed for use in many of the above-mentioned applications.

[0005] U.S. Patent No. 8,058,486, entitled "INTEGRATED PROCESS TO PRODUCE 2,3,3,3-TETRAFLUOROPROPENE" (issued November 15, 2011), U.S. Patent No. 8,975,454, entitled "PROCESS Various methods are known for producing HFO-134yf, such as those described in U.S. Patent No. 8,766,020, entitled "PROCESS FOR PRODUCING 2,3,3,3-TETRAFLUOROPROPENE," issued March 10, 2015, and U.S. Patent No. 8,766,020, entitled "PROCESS FOR PRODUCING 2,3,3,3-TETRAFLUOROPROPENE," issued July 1, 2014, the entireties of which are incorporated herein by reference. Summary of the Invention [Problem to be solved by the invention]

[0006] Because the production of 2,3,3,3-tetrafluoropropene can potentially suffer from many undesirable side reactions, there is a need for compositions and methods that allow for improved yields, more economical processes, and limited waste production in the production of 2,3,3,3-tetrafluoropropene and subsequent processing. [Means for solving the problem]

[0007] The present disclosure provides various manufacturing processes and

[0003] The present invention provides a composition containing propane (HCFC-244bb) and at least one impurity. Such a composition may be useful for the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf or 1234yf). Such a method and composition may enable the production of HFO-1234yf with acceptable yields, a sufficiently economical process, and acceptable levels of waste production.

[0008] Such compositions include HCFC-244bb and 2,3,3,3-tetrafluoropropene (HFO-1234yf), pentafluoropropene (HFO-1225ye isomer(s)), 1,3,3,3-tetrafluoropropene (HFO-1234ze isomer(s)), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,1,2-tetrafluoropropane (HFC-254eb), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). , 1-chloro-1,1,2,2-tetrafluoropropane (HCFC-244cc), chlorotetrafluoropropene (HCFO-1224 isomer), E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zdE), 1,1,1,3,3-pentafluoropropane (HFC-245fa), heptafluorobutane (HFC-347 isomer), 2-chloro-1,1,1,3,3-pentafluoropropane (HFC-235da), 3-chloro-1,1,1,2-tetrafluoropropane ( HCFC-244eb), 3-chloro-3,3,3-trifluoropropane (HCFC-253fb), dichlorotrifluoropropene (HCFO-1223 isomer), 2,3-dichloro-1,1,1,2-tetrafluoropropane (HCFC-234bb), 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243db), chlorohexafluorobutene (HFO-1326 isomer), hexafluorobutene (HFO-1336 isomer), pentafluorobutene (HFO-1345 isomer ), heptafluorobutene (HFO-1327 isomers), tetrafluorohexane (HFC-5-11-4 isomers), 1,3,3,3-tetrafluoropropane (HFC-254fb), chlorohexafluorobutane (HFC-346 isomers), octafluoropentane (HFC-458 isomers), octafluorohexene, 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), (Z)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), C5H2F 10 isomers, C6H2F8 isomers, C6H4F8 isomers, decafluorobutane (C4F 10and at least one impurity comprising a long-chain halogenated hydrocarbon having a boiling point greater than about 15° C., such as a C6H3F7 isomer, a C6H3F9 isomer, a dichlorodifluoropropene (HCFO-1232 isomer), a trichlorotrifluoropropane (HCFC-233 isomer), a C6H3Cl2F7 isomer, a trichlorodifluoropropane (HCFC-242 isomer), a C8H3F7 isomer, or a long-chain halogenated hydrocarbon having a boiling point greater than about 15° C.

[0009] In various embodiments, the at least one impurity can be present in an amount of from about 0.0001% to about 2% by weight, from about 0.0005% to about 0.5% by weight, or from about 0.001% to about 0.05% by weight.

[0010] In some embodiments, the composition includes at least two different impurities. For example, in some embodiments, the at least two different impurities can include a first impurity, where the first impurity is 253fb. In some embodiments, one impurity can be a heptafluorobutane, such as 1,1,1,2,2,3,3-heptafluorobutane. In some embodiments, the combined amount of 253fb and heptafluorobutane, such as 253fb and heptafluorobutane, is present in an amount of 0.0005% to 0.5% by weight, 0.001% to 0.2% by weight, or 0.0015% to 0.12% by weight. [Brief explanation of the drawings]

[0011] The above-mentioned and other features and objects of the present disclosure, and the manner in which they are accomplished, will become more apparent, and the disclosure itself will be better understood, by referring to the following description of exemplary embodiments of the present disclosure in combination with the accompanying drawings.

[0012] [Figure 1A] FIG. 1 is a process flow diagram showing exemplary portions of a process for producing 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0013] [Figure 1B]FIG. 1B is a process flow diagram similar to that shown in FIG. 1A, but additionally including a third distillation column in series.

[0014] [Figure 1C] FIG. 1B is a process flow diagram similar to the process flow shown in FIG. 1A showing an exemplary portion of a process for producing 2,3,3,3-tetrafluoropropene (HFO-1234yf) using a side stream from a distillation column.

[0015] [Figure 2] FIG. 1 is a process flow diagram showing step 3 of an exemplary process for producing HFO-1234yf.

[0016] Corresponding reference characters indicate corresponding parts throughout the several views. The drawings, while depicting embodiments of the present disclosure, are not necessarily to scale, and certain features may be exaggerated to better illustrate and explain the present disclosure. The exemplifications set forth herein illustrate representative embodiments of the present disclosure in various forms, and such exemplifications should not be construed as limiting the scope of the present disclosure in any manner. DETAILED DESCRIPTION OF THE INVENTION

[0017] As briefly described above, the present disclosure provides various compositions suitable for the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf or 1234yf). The production of HFO-1234yf from 1,1,2,3 tetrachloropropene (TCP) and hydrogen fluoride can be generalized in a three-step process.

[0018] Step 1 can be understood as producing 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) from 1,1,2,3-tetrachloropropene (1230xa) in a vapor phase reactor according to the following reaction scheme: [ka]

[0019] Step 2 can be understood as producing 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) from 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) in a reactor, such as a liquid phase reactor, according to the following reaction scheme: [ka]

[0020] Step 3 can be understood as producing 2,3,3,3-tetrafluoropropene (HFO-1234yf) from 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) in a reactor, such as a vapor phase reactor, according to the following reaction scheme: [ka]

[0021] Without being bound by any particular theory of operation, certain embodiments of the present disclosure are based on the observation and understanding that during certain dehydrochlorination reactions of certain dehydrochlorination starting materials, such as 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), to produce 2,3,3,3-tetrafluoropropene (HFO-1234yf) (during step 3), the presence of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) in the reaction starting material, such as the HCFC-244bb feedstock, can result in a dramatic reduction in the conversion of HCFC-244bb to HFO-1234yf and an increase in the formation of 3,3,3-trifluoropropyne (CFCCH), which is the dehydrochlorination product of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

[0022] These results are disadvantageous in that they result in lower yields of the desired product, and with respect to the formation of the 3,3,3-trifluoropropyne (CF3CCH) by-product, they are even more disadvantageous in that this by-product is a flammable gas and is toxic, and therefore undesirable.

[0023] For example, the presence of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb or 253fb) in the step 3 reactor can result in the formation and / or presence of elevated concentrations of both 3,3,3-trifluoropropene (HFO-1243zf or 1243zf) and vinyl chloride (1140), which can then be found in the crude 1234yf product. The presence of 1243zf and 1140 impurities can result in additional yield loss during final purification steps, which is undesirable due to the difficulty of separating 1243zf and 1140 from 1234yf.

[0024] Also, the presence of high boiling point solvents and tars (which are long chain halogenated hydrocarbons) formed as a side reaction in the Step 3 reactor appears to either cause excessive coking of the Step 3 reactor or make the reactor more susceptible to coking, leading to premature failure of the reactor. Non-limiting examples of high boiling point solvents include C4F 10 , C5H2F 10 These high boiling point solvents include, but are not limited to, various tetrafluorohexane isomers, C6H3F7 isomers, C6H3Cl2F7 isomers, C6H2F8 isomers, C6H4F8 isomers, C6H3F9 isomers, various octafluorohexene isomers, and C8H3F7 isomers. These high boiling point solvents can further react to form tars, which can condense to form a dark brown or black viscous liquid upon cooling.

[0025] However, some impurities prior to dehydrochlorination in Step 3 (as shown in FIG. 2 as dehydrochlorination reactor 72) may result in an acceptable, economical process. Surprisingly, it has been discovered that the compositions disclosed herein containing HCFC-244bb and certain impurities may be suitable starting compositions for Step 3, even with the presence of some impurities. Non-limiting examples of such impurities include 1-chloro-1,1,2,2-tetrafluoropropane (HCFC-244cc), E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zdE), and heptafluorobutane (HFC-347 isomers).

[0026] The embodiments disclosed below are not intended to be exhaustive or to limit the disclosure to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that others skilled in the art can utilize their teachings.

[0027] Compositions useful as feedstocks for step 3 include 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 2,3,3,3-tetrafluoropropene (HFO-1234yf), pentafluoropropene (HFO-1225ye isomer(s)), 1,3,3,3-tetrafluoropropene (HFO-1234ze isomer(s)), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,1,2-tetrafluoropropane (HFC-254eb), 2-chloro-3, 3,3-Trifluoropropene (HCFO-1233xf), 1-chloro-1,1,2,2-tetrafluoropropane (HCFC-244cc), chlorotetrafluoropropene (HCFO-1224 isomer), E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zdE), 1,1,1,3,3-pentafluoropropane (HFC-245fa), heptafluorobutane (HFC-347 isomer), 2-chloro-1,1,1,3,3-pentafluoropropane (HFC-235da), 3-chloro-1, 1,1,2-tetrafluoropropane (HCFC-244eb), 3-chloro-3,3,3-trifluoropropane (HCFC-253fb), dichlorotrifluoropropene (HCFO-1223 isomer), 2,3-dichloro-1,1,1,2-tetrafluoropropane (HCFC-234bb), 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243db), chlorohexafluorobutene (HFO-1326 isomer), hexafluorobutene (HFO-1336 isomer), pentafluorobutene (HF O-1345 isomers), heptafluorobutene (HFO-1327 isomers), tetrafluorohexane (HFC-5-11-4 isomers), 1,3,3,3-tetrafluoropropane (HFC-254fb), chlorohexafluorobutane (HFC-346 isomers), octafluoropentane (HFC-458 isomers), octafluorohexene, 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), (Z)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), C5H2F 10 isomers, C6H2F8 isomers, C6H4F8 isomers, decafluorobutane (C4F10 ), C6H3F7 isomers, C6H3F9 isomers, dichlorodifluoropropene (HCFO-1232 isomers), trichlorotrifluoropropane (HCFC-233 isomers), C6H3Cl2F7 isomers, trichlorodifluoropropane (HCFC-242 isomers), C8H3F7 isomers, or tars that are long chain halogenated hydrocarbons.

[0028] For example, compositions containing 244bb may also have one or more of the impurities discussed below. Such compositions may have HCFC-244bb present in an amount of at least 95.0 wt%, at least 97 wt%, or at least 98 wt%, and up to 99.9995 wt%, up to 99.0000 wt%, or up to 98.1 wt%, or any combination thereof, such as 95.0 wt% to 99.9995 wt%, 97 wt% to 99.0000 wt%, 95.0 wt% to 98.1 wt%, or 98.0 wt% to 99.0 wt%.

[0029] In particular, 253fb may be present in an amount of at least 0.0001 wt.%, at least 0.0005 wt.%, at least 0.001 wt.%, and at least 0.0015 wt.%, as well as up to 0.05 wt.%, up to 0.03 wt.%, up to 0.02 wt.%, up to 0.01 wt.%, up to 0.005 wt.%, or any combination thereof, such as 0.0001 wt.% to 0.05 wt.%, 0.0001 wt.% to 0.03 wt.%, 0.0005 wt.% to 0.02 wt.%, 0.001 wt.% to 0.01 wt.%, or 0.0015 wt.% to 0.005 wt.%.

[0030] In the aforementioned composition, the total sum of lights, including without excluding 2,3,3,3-tetrafluoropropene (HFO-1234yf), pentafluoropropene (HFO-1225ye isomer(s)), 1,3,3,3-tetrafluoropropene (HFO-1234ze isomer(s)), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,1,2-tetrafluoropropane (HFC-254eb), is at least 0.0005% by weight, ... The concentration may be at least 0.001% by weight and at least 0.0015% by weight, as well as up to 0.5% by weight, up to 0.2% by weight, up to 0.1% by weight, up to 0.05% by weight, up to 0.01% by weight, or any combination thereof, such as 0.0005% to 0.5% by weight, 0.0005% to 0.2% by weight, 0.0005% to 0.1% by weight, 0.001% to 0.05% by weight, or 0.0015% to 0.01% by weight.

[0031] HCFC-1233xf may be present in an amount of at least 0.05 wt%, at least 0.1 wt%, and at least 0.2 wt%, as well as up to 5.0 wt%, up to 3.0 wt%, up to 2.0 wt%, or any combination thereof, such as 0.05 wt% to 5.0 wt%, 0.1 wt% to 3.0 wt%, or 0.2 wt% to 2.0 wt%.

[0032] HCFC-244cc may be present in an amount of at least 0.0005 wt%, at least 0.001 wt%, and at least 0.0015 wt%, as well as up to 0.5 wt%, up to 0.2 wt%, up to 0.1 wt%, or any combination thereof, such as 0.0005 wt% to 0.5 wt%, 0.001 wt% to 0.2 wt%, or 0.0015 wt% to 0.1 wt%.

[0033] HCFO-1224 may be present in an amount of at least 0.0001 wt.%, at least 0.0002 wt.%, and at least 0.0003 wt.%, and up to 0.01 wt.%, up to 0.005 wt.%, up to 0.003 wt.%, up to 0.002 wt.%, or any combination thereof, such as 0.0001 wt.% to 0.01 wt.%, 0.0001 wt.% to 0.005 wt.%, 0.0002 wt.% to 0.003 wt.%, or 0.0003 wt.% to 0.002 wt.%.

[0034] HCFO-1233zdE is at least 0.0001 wt%, at least 0.0002 wt%, and at least 0.0005 wt%, and up to 0.05 wt%. It may be present in an amount up to 0.02% by weight, up to 0.01% by weight, or any combination thereof, such as 0.0001% to 0.05% by weight, 0.0002% to 0.02% by weight, or 0.0005% to 0.01% by weight.

[0035] HFC-245fa may be present in an amount of at least 0.0005 wt.%, at least 0.001 wt.%, and at least 0.0015 wt.%, as well as up to 1.0 wt.%, up to 0.5 wt.%, up to 0.1 wt.%, up to 0.05 wt.%, up to 0.01 wt.%, or any combination thereof, such as 0.0005 wt.% to 1.0 wt.%, 0.0005 wt.% to 0.5 wt.%, 0.0005 wt.% to 0.1 wt.%, 0.001 wt.% to 0.05 wt.%, or 0.0015 wt.% to 0.01 wt.%.

[0036] In some embodiments, the HFC-347 isomer may be present in an amount of at least 0.0005 wt.%, at least 0.001 wt.%, and at least 0.0015 wt.%, as well as up to 0.5 wt.%, up to 0.2 wt.%, up to 0.1 wt.%, up to 0.05 wt.%, up to 0.02 wt.%, or any combination thereof, such as 0.0005 wt.% to 0.5 wt.%, 0.0005 wt.% to 0.2 wt.%, 0.001 wt.% to 0.05 wt.%, or 0.0015 wt.% to 0.02 wt.%.

[0037] HCFC-235da may be present in an amount of at least 0.0001 wt%, at least 0.0005 wt%, and at least 0.001 wt%, as well as up to 0.02 wt%, up to 0.01 wt%, up to 0.005 wt%, up to 0.003 wt%, up to 0.002 wt%, or any combination thereof, such as 0.0001 wt% to 0.02 wt%, 0.0001 wt% to 0.01 wt%, 0.0005 wt% to 0.005 wt%, or 0.001 wt% to 0.003 wt%.

[0038] HCFC-244eb may be present in an amount of at least 0.0001 wt%, at least 0.0005 wt%, and at least 0.001 wt%, as well as up to 0.05 wt%, up to 0.03 wt%, up to 0.02 wt%, up to 0.01 wt%, up to 0.005 wt%, or any combination thereof, such as 0.0001 wt% to 0.05 wt%, 0.0001 wt% to 0.03 wt%, 0.0001 wt% to 0.02 wt%, 0.0005 wt% to 0.01 wt%, or 0.001 wt% to 0.005 wt%.

[0039] HCFC-234bb may be present in an amount of at least 0.0001 wt%, at least 0.0005 wt%, and at least 0.001 wt%, as well as up to 0.1 wt%, up to 0.05 wt%, up to 0.03 wt%, up to 0.02 wt%, up to 0.01 wt%, or any combination thereof, such as 0.0001 wt% to 0.1 wt%, 0.0001 wt% to 0.05 wt%, 0.0005 wt% to 0.03 wt%, 0.0005 wt% to 0.02 wt%, or 0.001 wt% to 0.01 wt%.

[0040] HCFC-243db may be present in an amount of at least 0.0001 wt%, at least 0.0005 wt%, and at least 0.001 wt%, as well as up to 0.05 wt%, up to 0.02 wt%, up to 0.01 wt%, up to 0.005 wt%, up to 0.003 wt%, or any combination thereof, such as 0.0001 wt% to 0.05 wt%, 0.0005 wt% to 0.02 wt%, 0.001 wt% to 0.01 wt%, or 0.0015 wt% to 0.005 wt%.

[0041] Chlorohexafluorobutene (HFO-1326 isomers), hexafluorobutene (HFO-1336 isomers), pentafluorobutene (HFO-1345 isomers), heptafluorobutene (HFO-1327 isomers), tetrafluorohexane (HFC-5-11-4 isomers), 1,3,3,3-tetrafluoropropane (HFC-254fb), chlorohexafluorobutane (HFC-346 isomers), octafluoropentane (HFC-458 isomers), octafluorohexene, 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), (Z)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), C5H2F 10 isomers, C6H2F8 isomers, C6H4F8 isomers, decafluorobutane (C4F 10), C6H3F7 isomers, C6H3F9 isomers, dichlorodifluoropropenes (HCFO-1232 isomers), trichlorotrifluoropropanes (HCFC-233 isomers), C6H3Cl2F7 isomers, trichlorodifluoropropanes (HCFC-242 isomers), C8H3F7 isomers and the total of heavy fractions, including without excluding tar, is at least 0.0005% by weight, at least 0.001% by weight and at least 0.0015% by weight. % by weight, as well as up to 5.0% by weight, up to 2.0% by weight, up to 1.0% by weight, up to 0.5% by weight, up to 0.3% by weight, up to 0.1% by weight, or any combination thereof, such as 0.0005% to 2.0% by weight, 0.0005% to 1.0% by weight, 0.0005% to 0.5% by weight, 0.001% to 0.3% by weight, or 0.0015% to 0.1% by weight.

[0042] The total amount of impurities or combinations of impurities is not particularly limited and may be present in an amount of at least 0.0001 wt%, at least 0.0002 wt%, and at least 0.0003 wt%, as well as up to 5.0 wt%, up to 3.0 wt%, up to 2.0 wt%, up to 1.0 wt%, up to 0.5 wt%, or any combination thereof, such as 0.0001 wt% to 5.0 wt%, 0.0001 wt% to 3.0 wt%, 0.0001 wt% to 2.0 wt%, 0.0002 wt% to 1.0 wt%, or 0.0003 wt% to 0.5 wt%, etc. For example, in some embodiments where the composition may have two or more impurities, the total impurities may be present within the ranges described above. By way of non-limiting example, the composition may have both the 253fb and 347 isomers in a combined amount present at least 0.0005%, at least 0.001%, and at least 0.0015%, as well as up to 0.5%, up to 0.2%, up to 0.1%, up to 0.05%, up to 0.02%, or any combination thereof, such as 0.0005% to 0.5%, 0.0005% to 0.2%, 0.001% to 0.05%, or 0.0015% to 0.02% by weight. In one example, a composition having 0.022% by weight of 253fb and 0.0186% by weight of 347 is in the range of 0.001% to 0.05% by weight. In another example, a composition having 0.003 wt% 253fb and 0.1139 wt% 347 is in the range of 0.0005 wt% to 0.2 wt%.

[0043] As used herein, the modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes at least the degree of error associated with measurement of the particular quantity). When used in the context of a range, the modifier "about" should also be considered to represent the range defined by the absolute values ​​of the two endpoints. For example, the range "about 2 to about 4" also represents a range of "2 to 4."

[0044] 1A is a process flow diagram illustrating an exemplary manufacturing process flow 1 according to various embodiments. HF feed 5 and 1233xf feed 3 (from step 1) may be combined, for example, in any pipe or tube, such as combination flow valve 28, heated by heat exchanger 24, and then fed to reactor 2 as stream 7. In reactor 2, which may be shown in FIG. 1A as a liquid-phase reactor, HCFC-244bb is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCl, which is reacted with HCFC ... After the step 2 reaction takes place in reactor 2, crude HCFC-244bb product stream 9 is sent to catalyst stripper column 4, where the catalyst is separated and returned to reactor 2 via return stream 18. After treatment in catalyst stripper column 4 and heat exchanger 22, stripped crude HCFC-244bb product stream 11 is sent to lights column 6. In the lights column, light boiling products are distilled as lights overhead stream 13, while lights bottoms stream 15 can be cooled by heat exchanger 16 and sent to phase separator 8 via stream 24, where HF is separated from lights bottoms stream 15. The HF phase can then be returned to the step 2 reactor as recycled HF stream 19, and liquid stream 17 containing HCFC-244bb can be sent to one or more distillation columns.

[0045] FIG. 1A shows liquid stream 17 initially sent to azeotropic distillation column 10. In azeotropic distillation column 10, HCFO-1233xf can be removed from the HCFC-244bb liquid stream using azeotropic distillation. To this end, a third stream, such as unreacted reagents and / or by-products from step 3, may be provided via recycle stream 29, forming an azeotropic mixture or azeotropic composition and then isolated from the composition. More specifically, the presence of a third component (e.g., HF) may form an azeotrope and / or binary azeotrope with HCFO-1233xf and / or HCFC-244bb. Standard separation means, such as distillation in azeotropic distillation column 10, can be used to separate the various azeotropes from solution, whereby a significant portion of the HCFC-244bb remains in solution in azeotropic bottoms 21.

[0046] In various embodiments of the present disclosure, compositions are provided that include effective amounts of HF, light organics, heavy organics, or combinations thereof to form azeotropic or azeotrope-like compositions. As used herein, the term "effective amount" refers to the amount of each component that, when combined with the other components, results in the formation of an azeotrope or azeotrope-like mixture. As used herein, the terms "heteroazeotrope" and "heteroazeotrope" refer to the amount of each component that, when combined with the other components, results in the formation of an azeotrope or azeotrope-like mixture. A "heterogeneous azeotrope" is an azeotropic mixture that contains two liquid phases and a vapor phase that exists simultaneously. It includes compound-like compositions.

[0047] Such azeotropes and methods of azeotropic separation or distillation may further include those disclosed in U.S. Pat. No. 7,803,283 and U.S. Patent Application Publication Nos. 2010 / 0187088 and 2009 / 0256110, the entire contents of each of which are incorporated herein by reference.

[0048] Azeotropic bottoms 21 may then be isolated in heavies column 12 as purified HCFC-244bb substantially free of 253fb and other heavy impurities, shown as purified HCFC-244bb overhead stream 27, which may be sent for further processing (e.g., step 3) and / or storage. Azeotropic overhead stream 23 may then be recycled back to reactor 2 for reuse in step 2 or may be combined with feed stream 7, e.g., piping or tubing, such as a combination of flow valves 28.

[0049] Finally, bottoms 25 from heavies column 12, which may contain concentrated 253fb and tar and / or other heavy boiling point solvents, may be collected and subjected to additional recovery to improve yield and / or disposal. As used herein, the term "heavy boiling point solvent" may include organic compositions having a boiling point above 244bb, which have a normal boiling point of about 14-15°C. For example, in some embodiments, heavy organics may have a boiling point above about 15°C. Heavy organics include HCFC-253fb, C4F 10 , C5H2F10 isomers, various tetrafluorohexane isomers, C6H3F7 isomers, C6H3Cl2F7 isomers, C6H2F8 isomers, C6H4F8 isomers, C6H3F9 isomers, various octafluorohexene isomers, C8H3F7 isomers, tar, or combinations thereof.

[0050] As used herein, the term "heavy boiling point solvent" may include organic compositions having a boiling point above 244bb, which have a normal boiling point of about 14-15°C. For example, in some embodiments, heavy organics may have a boiling point above about 15°C. Heavy organics include HCFC-253fb, CF4 10 , C5H2F 10 isomers, various tetrafluorohexane isomers, C6H3F7 isomers, C6H3Cl2F7 isomers, C6H2F8 isomers, C6H4F8 isomers, C6H3F9 isomers, various octafluorohexene isomers, C8H3F7 isomers, tar, or combinations thereof.

[0051] Thus, in embodiments such as the process flow diagrams shown in Figures 1A-1C, the impurities removed include 1-chloro-3,3,3-trifluoropropane (HCFC-253fb), 1,1,1,3,3-pentafluoropropane (HFC-245fa), heptafluorobutane (HFC-347), chlorohexafluorobutene (HFO-1326 isomers), hexafluorobutene (HFO-1336 isomers), pentafluorobutene (HFO-1345 isomers), heptafluorobutene (HFO-1327 isomers), 1-chloro-1,1,2,2-tetrafluoropropane (HCFC-244cc), 2,3-dichloro-1,1,1,2-tetrafluoropropane (HFC-234bb), chlorotetrafluoropropene (HCFO-1224 isomers), tetrafluoropropene (HFC ...ane (HFC-1224 isomers), tetrafluoropropane (HFC-1224 isomers), tetrafluoropropane (HFC-1224 isomers), tetrafluoropropane (HFC-1224 isomers), tetrafluoropropane (HFC-1224 isomers), tetrafluoropropane (HFC-1224 isomers), tetrafluoropropane (HFC-1224 isomers), tetra tetrafluorohexane (HFC-5-11-4 isomer), tetrafluoropropane (HFC-254 isomer), chlorohexafluorobutane (HFC-346 isomer), octafluoropentane (HFC-458 isomer), chlorotrifluoropropene (HCFO-1233 isomer), (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), 2-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235da), octafluorohexene, 3-chloro-1,1,1,2-tetrafluoropropane (HFC-244eb), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), (Z)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), C5H2F 10 isomers, C6H2F8 isomers, C6H4F8 isomers, decafluorobutane (C4F 10 ), C6H3F7 isomers, C6H3F9 isomers, dichlorodifluoropropenes (HCFO-1232 isomers), dichlorotrifluoropropenes (HCFO-1223 isomers), dichlorotetrafluoropropanes (HCFC-234 isomers), dichlorotrifluoropropanes (HCFC-243 isomers), trichlorotrifluoropropanes (HCFC-233 isomers), C6H3Cl2F7 isomers, trichlorodifluoropropanes (HCFC-242 isomers), C8H3F7 isomers, tar, or combinations thereof.

[0052] In some embodiments, such as process flow 30 shown in FIG. 1B, which includes many aspects similar to or identical to those of FIG. 1A, bottoms 25 from heavies column 12 may be further separated, such as in distillation column 32. In some embodiments, heavies recovery column 32 may further separate high boiling solvents and tars from heavies column 12 into overhead 33 and bottoms 35. In various embodiments, heavies recovery column 32 may operate by batch distillation, while in other embodiments, distillation column 32 may be operated by continuous distillation. Also, in some embodiments, purified or partially purified 244bb may be stored in a storage vessel, such as storage vessel 60.

[0053] Some embodiments, such as process flow 40 shown in Figure 1C, include many aspects similar or identical to Figure 1A, but use a side stream 47 of distillation column 10 to illustrate the separation of refined 244bb. In some embodiments, the use of a side stream can be beneficial due to differential separation within various trays of distillation column 10 due to vapor pressure differences between the high boiling solvents, tar, and refined 244bb.

[0054] Distillation column 12 in FIGS. 1A-1C and distillation column 32 in FIG. 1B can be operated in either batch mode or continuous mode. The conditions for these columns depend on the particular range, practicality of the column being used, and both operational and equipment costs. Distillation column 12 and / or distillation column 32 are operated to achieve optimal separation of the 244 bbl from impurities using conventional distillation and / or a series of distillations. Exemplary processes include decantation, centrifugation, liquid-liquid extraction, distillation, flash distillation, partial vaporization, partial condensation, or a combination thereof.

[0055] Such compositions may be useful in the production of 2,3,3,3-tetrafluoropropene (1234yf). For example, Figure 2 shows a process flow diagram 70 illustrating the production of 1234yf from a feed containing purified 244bb and at least one impurity. Process flow diagram 70 in Figure 2 includes an input stream 27 containing HCFC-244bb, which may contain at least one of the impurities described above, as exemplified in the description of Figures 1A and 1B.

[0056] The composition containing HCFC-244bb and at least one of the aforementioned impurities may then be heated by heat exchanger 24 (as briefly described above in FIG. 3 ) and sent to dehydrochlorination reactor 72 to produce 1234yf. Reaction product stream 75 containing 1234yf may then be sent to recycle column 62, where bottoms 63 may be recycled back to reactor 72 and / or returned to azeotropic distillation column 10 of step 2 as stream 29 in FIGS. 1A and 1B , and overhead 65 may be sent to be washed with HCl stream 67 in HCl column 64. HCl wash stream 69 may then be washed with solution stream 77 in scrubber 74. Solution stream 77 may be a solution such as a caustic or acidic solution, such as a solution containing water or sulfuric acid. Wash product stream 79 may then be sent to dryer 76 to remove any wash solution that may remain.

[0057] Dried product stream 81 may then be distilled in lights column 78, and overhead lights stream 83 may be recycled or removed through heat exchanger 22. Lights bottoms stream 85 may be heated or cooled via heat exchanger 26 and further distilled in product distillation column 80. Purified 1234yf stream 87 may be processed through heat exchanger 22, stored in vessel 82, and / or recycled. Product bottoms stream 29 may be heated in heat exchanger 26 and recycled back into product distillation column 80 and / or removed for waste.

[0058] Dehydrochlorination of HCFC-244bb may be carried out at temperatures ranging from 200°C to 800°C, preferably 300°C to 600°C, more preferably 425°C to 525°C, and at pressures ranging from 0 to 300 psig, preferably 5 to 200 psig, more preferably 20 to 100 psig. The residence time of HCFC-244bb in the reactor may range from about 1 second to about 320 seconds, although longer or shorter times can be used. [Example]

[0059] The unit, including all unit operations as described in Figure 1A, was operated for one month. During operation, organic samples were taken daily from process streams 17, 21, and 27 for GC and GCMS analysis. Table 1 shows the average organic composition of these three streams. [Table 1] 1 In addition to 1233xf, other non-limiting examples of lights include 2,3,3,3-tetrafluoropropene (HFO-1234yf), pentafluoropropene (HFO-1225ye isomer(s)), 1,3,3,3-tetrafluoropropene (HFO-1234ze isomer(s)), 1,1,1,2,2-pentafluoropropane (HFC-245cb), and 1,1,1,2-tetrafluoropropane (HFC-254eb). 2In addition to those listed in Table 1 after the 244bb component, other non-limiting examples of heavier fractions include chlorohexafluorobutene (HFO-1326 isomers), hexafluorobutene (HFO-1336 isomers), pentafluorobutene (HFO-1345 isomers), heptafluorobutene (HFO-1327 isomers), tetrafluorohexane (HFC-5-11-4 isomers), 1,3, 3,3-Tetrafluoropropane (HFC-254fb), chlorohexafluorobutane (HFC-346 isomers), octafluoropentane (HFC-458 isomers), octafluorohexene, 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), (Z)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), C5H2F 10 isomers, C6H2F8 isomers, C6H4F8 isomers, decafluorobutane (C4F 10 ), C6H3F7 isomers, C6H3F9 isomers, dichlorodifluoropropene (HCFO-1232 isomers), trichlorotrifluoropropane (HCFC-233 isomers), C6H3Cl2F7 isomers, trichlorodifluoropropane (HCFC-242 isomers), C8H3F7 isomers, and tar.

[0060] While this disclosure has been described as having exemplary designs, the disclosure may be further modified within the spirit and scope of the disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the disclosure using its general principles. Further, this application is not intended to cover any variations, uses, or adaptations of the disclosure using its general principles. It is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which the disclosure pertains.

[0061] Furthermore, the connecting lines shown in the various figures contained herein are intended to illustrate example functional relationships and / or physical couplings between the various elements. It should be noted that many alternative or additional functional relationships or physical connections may exist in a practical system. However, benefits, advantages, solutions to problems, and any elements that may cause or enhance any benefit, advantage, or solution should not be construed as critical, necessary, or essential features or elements. Accordingly, the scope is not limited except by the appended claims, and references to elements in the singular are not intended to mean "one and only one," unless expressly stated otherwise, but rather "one or more." Furthermore, when phrases similar to "at least one of A, B, or C" are used in the claims, the phrase is intended to mean that A may be present alone in one embodiment, B may be present alone in one embodiment, C may be present alone in one embodiment, or any combination of elements A, B, or C (e.g., A and B, A and C, B and C, or A and B and C) may be present in a single embodiment.

[0062] In the detailed description herein, references to "one embodiment," "an embodiment," "an example embodiment," etc. indicate that the described embodiment may include a particular feature, structure, or characteristic, but that not all embodiments necessarily include the particular feature, structure, or characteristic. Moreover, such phrases do not necessarily refer to the same embodiment. It should be noted that when a particular feature, structure, or characteristic is described in connection with one embodiment, it is submitted that it is within the knowledge of one of ordinary skill in the art with the benefit of this disclosure to affect such feature, structure, or characteristic in connection with other embodiments, whether or not explicitly stated. After reading the description, it will be apparent to one of ordinary skill in the art how to implement the present disclosure in alternative embodiments.

[0063] It should be noted that any element, component, or method step in this disclosure is intended to be disclosed herein regardless of whether the element, component, or method step is expressly recited in a claim. No claim element herein is to be construed under the provisions of 35 U.S.C. 112(f) unless the element is expressly recited using the word "means for." As used herein, the terms "comprises," "comprising," or their equivalents are not intended to be limiting. Any other variation of is intended to cover a non-exclusive inclusion, whereby a process, method, article, or apparatus that includes a recitation of elements does not include only those elements, but may also include other elements not expressly recited or inherent to such process, method, article, or apparatus.

Claims

1. 1. A composition comprising: 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and at least one impurity comprising at least one of chlorotetrafluoropropenes (HCFO-1224 isomers), heptafluorobutanes (HFC-347 isomers), 1,3,3,3-tetrafluoropropane (HFC-254fb), and trichlorotrifluoropropanes (HCFC-233 isomers).

2. 10. The composition of claim 1, wherein the at least one impurity is present in an amount of from about 0.0001% to about 2.0% by weight.

3. 3. The composition of claim 2, wherein the at least one impurity is present in an amount of from about 0.0005% to about 0.5% by weight.

4. 4. The composition of claim 3, wherein the at least one impurity is present in an amount of from about 0.001% to about 0.05% by weight.

5. 10. The composition of claim 1, wherein the composition comprises at least two different impurities.

6. 6. The composition of claim 5, wherein the at least two different impurities include a first impurity, and the first impurity is 253fb.

7. 10. The composition of claim 1, wherein the at least one impurity is heptafluorobutane.

8. The composition of claim 7, wherein the heptafluorobutane is 1,1,1,2,2,3,3-heptafluorobutane.

9. 7. The composition of claim 6, wherein the second impurity is heptafluorobutane.

10. 10. The composition of claim 9, wherein the combined amount of 253fb and heptafluorobutane is present in an amount of 0.0005% to 0.5% by weight.

11. 11. The composition of claim 10, wherein the combined amount of 253fb and heptafluorobutane is present in an amount of 0.001% to 0.2% by weight.

12. 12. The composition of claim 11, wherein the combined amount of 253fb and heptafluorobutane is present in an amount of 0.0015% to 0.12% by weight.

13. 10. The composition of claim 1, wherein said HCFC-244bb is present in an amount of from 95% to 99.999% by weight.

14. 10. The composition of claim 1, wherein said HCFC-244bb is present in an amount of from 98.0% to 99.0% by weight.

15. The composition further comprising: 2,3,3,3-tetrafluoropropene (HFO-1234yf), pentafluoropropene (HFO-1225ye isomer(s)), 1,3,3,3-tetrafluoropropene (HFO-1234ze isomer(s)), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,1,2-tetrafluoropropane (HFC-254eb), 2-chloro-3,3,3-trifluoropropene (H CFO-1233xf), 1-chloro-1,1,2,2-tetrafluoropropane (HCFC-244cc), E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zdE), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 2-chloro-1,1,1,3,3-pentafluoropropane (HFC-235da), 3-chloro-1,1,1,2-tetrafluoropropane (HCFC-2 44eb), 3-chloro-3,3,3-trifluoropropane (HCFC-253fb), dichlorotrifluoropropene (HCFO-1223 isomer), 2,3-dichloro-1,1,1,2-tetrafluoropropane (HCFC-234bb), 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243db), chlorohexafluorobutene (HFO-1326 isomer), hexafluorobutene (HFO-13 36 isomer), pentafluorobutene (HFO-1345 isomer), heptafluorobutene (HFO-1327 isomer), tetrafluorohexane (HFC-5-11-4 isomer), chlorohexafluorobutane (HFC-346 isomer), octafluoropentane (HFC-458 isomer), octafluorohexene, 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), (Z)-1-chloro-3,3,10. The composition of claim 1, further comprising at least one additional impurity selected from 3-trifluoropropene (HCFO-1233zd(Z)), C5H2F10 isomers, C6H2F8 isomers, C6H4F8 isomers, decafluorobutane (C4F10), C6H3F7 isomers, C6H3F9 isomers, dichlorodifluoropropenes (HCFO-1232 isomers), C6H3Cl2F7 isomers, trichlorodifluoropropanes (HCFC-242 isomers), C8H3F7 isomers, or long-chain halogenated hydrocarbons having a boiling point greater than about 15°C.

16. A method for producing 2,3,3,3-tetrafluoropropene (HFO-1234yf) from the composition according to any one of claims 1 to 15.

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