Process for the removal of haloalkyne impurities from (HYDRO)halocarbon compositions

Abstract

The present invention relates to a method comprising contacting a composition comprising a (hydro)halocarbon and a compound of the formula Rf-C=CX (wherein Rf is a perfluorinated alkyl group and X is H, F, Cl, Br, or I) with a basic solution comprising a hydroxide, an alkoxide, and / or an amide to reduce the concentration of the formula Rf-C=CX (wherein Rf is a perfluorinated alkyl group and X is H, F, Cl, Br, or I). The present invention also comprises the steps of: (i) converting a starting material into a composition comprising a (hydro)halocarbon and a compound of the formula Rf-C≡CX (wherein Rf is a perfluorinated alkyl group and X is H, F, Cl, Br, or I) in the presence of HF and / or a catalyst; (ii) contacting the composition with a basic solution comprising a hydroxide, an alkoxide, and / or an amide to reduce the concentration of the compound of the formula Rf-C≡CX; The invention relates to a method for producing (hydro)halocarbons, comprising the step of (iii) recovering (hydro)halocarbons.

Description

Technology Field

[0001] The present invention relates to a composition comprising at least one (hydro)halocarbon, wherein formula R f This relates to a process for reducing the concentration of a compound of -C≡CX. Background Technology

[0002] The listing or discussion of previously published literature in this specification is not to be construed as an acknowledgment that such literature is part of the latest technology or is common knowledge.

[0003] (Hydro)halocarbons are commonly used as refrigerants or propellants and as blowing agents. Over the past 20 years, the various (hydro)halocarbons used in these fields have been changed because it was discovered that some of these substances (e.g., difluorodichloromethane, CFC-12) deplete the Earth's ozone layer, while others (e.g., 1,1,1,2-tetrafluoroethane, HFC-134a) act as unacceptable greenhouse gases.

[0004] Hydro(chloro)fluoroolefins have been shown to be a class of compounds capable of addressing these problems by having low ozone depletion potential and low global warming potential, while also providing good performance as refrigerants, propellant materials, and / or blowing agents.

[0005] For example, (hydro)fluoroalkenes, such as 2,3,3,3-tetrafluoropropene (HFO-1234yf), are increasingly being considered as working fluids in fields such as refrigeration, heat pumping, foam blowing, extinguishing agents / retarders, propellants, and solvency (e.g., plasma cleaning and etching). However, the processes used to manufacture (hydro)fluoroalkenes can result in the generation of toxic and / or other undesirable byproducts.

[0006] At elevated temperatures (e.g., above 300°C) that are typically considered essential to achieve commercially desired reaction rates in the production of hydro(chloro)fluoroolefins, various side reactions, including dehydrohalogenation, hydrohalogenation, and rearrangement, are possible. Accordingly, the mixture of raw products exiting the reaction train may contain various species in addition to the feed and the desired product.

[0007] For example, HFO-1234yf can be dehydrofluorinated under reaction conditions prepared to obtain 3,3,3-trifluoropropane (trifluoromethylacetylene, TFMA). Although byproducts such as TFMA may be formed in only small amounts relative to the desired product (e.g., HFO-1234yf), the presence of these byproducts in the HFO-1234yf composition can impair its toxicity, stability (chemical / oxidative), and / or compatibility with refrigeration system components such as hoses or lubricants. Consequently, some applications require very low levels of impurities. Unfortunately, some of the species formed possess physical properties very similar to the desired (hydro)halocarbon compound, or combine with it, rendering normal separation methods such as distillation or phase separation inefficient.

[0008] Accordingly, a novel method is required to remove reaction byproducts from (hydro)halocarbon compounds. means of solving the problem

[0009] In the first aspect of the present invention, (hydro)halocarbon and formula R f A composition comprising a compound of -C≡CX is brought into contact with a basic solution comprising a hydroxide, an alkoxide, and / or an amide, by R f -C≡CX(where R fA process is provided that includes reducing the concentration of (where X is a perfluorinated alkyl group and X is H, F, Cl, Br, or I).

[0010] As used herein, the terms “comprise, include,” “comprising, including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a process, method, article, or equipment comprising a list of components is not necessarily limited only to such components and may include other components not explicitly listed or inherent in such process, method, article, or equipment. Furthermore, unless otherwise explicitly stated, “or” refers to an inclusive or, not an exclusive or. For example, condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent); A is false (or absent) and B is true (or present); and both A and B are true (or present).

[0011] Additionally, the use of the singular form (“a” or “an”) is used to describe the components and elements described herein. This is merely for convenience and to provide a general meaning regarding the scope of the invention. This description should be read to include one or at least one, and the singular form also includes the plural form unless it is evident that it means otherwise.

[0012] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. In the event of a conflict, this specification, including definitions, shall be adopted. Methods and materials similar or equivalent to those described herein may be used in the practice or testing of embodiments of the invention, but suitable methods and materials are described below. Furthermore, materials, methods, and embodiments are merely illustrative and are not intended to be limiting.

[0013] When a quantity, concentration, or other value or parameter is provided as any one of a range, a preferred range, or a list of preferred upper and / or preferred lower limits, it should be understood as disclosing in detail any range formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the range is disclosed separately. Where numerical ranges are cited herein, unless otherwise stated, such ranges are intended to include their endpoints and all integers and fractions within such ranges. All percentage values ​​are by weight unless otherwise stated.

[0014] The term '(hydro)halocarbon' refers to any saturated or unsaturated hydrocarbon, wherein at least one hydrogen atom (and optionally, all hydrogen atoms) is replaced by a fluorine, chlorine, bromine, and / or iodine atom. In a preferred embodiment, the (hydro)halocarbon is unsaturated. To avoid doubt, the (hydro)halocarbon (and formula R f A composition containing a compound of -C≡CX may contain a single (hydro)halocarbon compound or a plurality of such compounds.

[0015] In a preferred embodiment, the (hydro)halocarbon is a hydrofluoroolefin (HFO). Preferably, the (hydro)halocarbon is C 3-7(Hydro)haloalkenes, e.g., C 3-4 It is a hydroxyhaloalkene. C 3-4 Examples of hydroxyhaloalkenes include hydrofluoropropene, hydrochlorofluoropropene, hydrofluorobutene, hydrochlorofluorobutene, and (hydro)fluoropropene. Advantageously, the (hydro)halocarbon is hydrohalopropene.

[0016] In one embodiment, the hydrohalopropene is tetrafluoropropene and / or chlorotrifluoropropene. The preferred tetrafluoropropene is 2,3,3,3-tetrafluoropropene (CF3CF=CH2, HFO-1234yf) and / or E, Z or E / Z-1,3,3,3-tetrafluoropropene (CF3CH=CHF, HFO-1234ze). The preferred chlorotrifluoropropene is E, Z or E / Z-1-chloro-3,3,3-trifluoropropene (CF3CH=CHCl, HCFO-1233zd) and / or 2-chloro-3,3,3-trifluoropropene (CF3CCl=CH2, HCFO-1233xf).

[0017] HFO-1234ze may exist as one of two configurational isomers, namely E or Z. As used herein, HFO-1234ze refers to the isomers, namely E-HFO-1234ze or Z-HFO-1234ze, as well as any combination or mixture of these isomers.

[0018] HCFO-1233zd may also exist as one of two coordination isomers, namely E or Z. As used herein, HCFO-1233zd refers to the isomers, namely E-HCFO-1233zd or Z-HCFO-1233zd, as well as any combination or mixture of these isomers.

[0019] Chemical formula R f In compounds of -C≡CX, R f is typically, C 1-5Perfluorinated alkyl group, preferably, C 1-2 It is a perfluorinated alkyl group, for example, a perfluorinated methyl group. In one embodiment, X is H, F, or Cl, preferably H and Cl. Preferred formula R f The compounds of -C≡CX are 1-chloro-3,3,3-trifluoropropine (CF3C≡CCl) and 3,3,3-trifluoropropine (CF3C≡CCl, trifluoromethylacetylene, TFMA).

[0020] It is known that alkynes such as TFMA can be produced by the dehydrohalogenation of hydrohaloalkenes by bases [e.g., literature ['March's Advanced Organic Chemistry' 6 th [See pages 1530 to 1532 of the Edition and EP-A-2143702]. Based on these teachings, (hydro)halocarbon and formula R f Rather, contacting a composition containing a compound of -C≡CX with a basic solution containing a hydroxide, alkoxide, and / or amide is R f It is expected that the concentration of -C≡CX will increase. However, surprisingly, the use of a basic solution containing a hydroxide, alkoxide, and / or amide from the composition as described above [reduces] the chemical formula R f It was discovered that at least a portion of the -C≡CX compound can be effectively removed.

[0021] To eliminate any doubt, it should be understood that the contact step of the present invention is distinguished from any initial step that may be adopted to produce a (hydro)halocarbon. For example, using a basic solution containing a hydroxide, the corresponding C 3-7 C by dehydrohalogenation of hydro(halo)fluoroalkenes 3-7The preparation of (hydro)fluoroalkenes is known [see, for example, WO 2008 / 075017]. The contact step of the process of the present invention is of formula R f Regardless of whether any compound of -C≡CX is also formed in this reaction step, C 3-7 It is distinguished from any reaction step in which a (hydro)fluoroalkene (or other (hydro)halocarbon) is formed (e.g., as described in WO 2008 / 075017).

[0022] A basic solution containing a hydroxide, alkoxide, and / or amide is used in the process of the present invention R f It is used to reduce the concentration of -C≡CX. Preferably, the base is one or more of alkali metal hydroxides, alkoxides or amides, alkaline earth metal hydroxides, alkoxides or amides, NR4OH, where R is independently H, C 1-10 alkyl, aryl (e.g., phenyl, naphthyl, or pyridinyl) or arylalkyl groups (e.g., benzyl or C 1-10 It is an alkyl-substituted phenyl.

[0023] Advantageously, the base is selected from potassium hydroxide (KOH), sodium hydroxide (NaOH), calcium hydroxide (Ca(OH)2), ammonium hydroxide (NH4OH), potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, and sodium amide (NaNH2). In a preferred embodiment, the base is sodium ethoxide, KOH, NaOH, or Ca(OH)2. Preferably, the base is KOH, NaOH, or Ca(OH)2. KOH and NaOH are currently most preferred.

[0024] The basic solution containing a hydroxide, alkoxide, and / or amide used in the contact step of the present invention typically has a concentration of about 0.1 to about 10 M, preferably about 0.2 to about 5 M, for example, about 0.5 to about 3 M, about 0.5 to about 2 M, or about 0.6 to about 2 M. Although not intended to be limited by theory, the identified concentration is of formula R f - To react with / remove from compounds of -C≡CX, sufficiently high and to avoid reacting with (hydro)halocarbons (e.g., additional R f It is considered to be sufficiently low to form -C≡CX.

[0025] In addition to this, it is believed that a lower concentration of basic solution has the advantage of reducing the possibility of precipitation of any corresponding fluoride salt (e.g., NaF, KF, etc.).

[0026] Typically, the solvent for the basic solution containing the hydroxide, alkoxide and / or amide used in the contact step is selected from water (i.e., aqueous solution), alcohols (e.g., methanol, ethanol, and n-propanol and i-propanol), diols, polyols (e.g., polyalkylene glycol, e.g., PEG300), polar aprotic solvents (e.g., diglym and N-methylpyrrolidone), ethers and cyclic ethers (e.g., diethyl ether, dibutyl ether, tetrahydrofuran), esters (e.g., methyl acetate, ethyl acetate, etc.), linear, branched, and cyclic alkanes (e.g., cyclohexane, methylcyclohexane), fluorinated derivatives thereof (e.g., hexafluoroisopropanol, perfluorotetrahydrofuran), and mixtures thereof. In a preferred embodiment, the solvent is selected from water, alcohols, and mixtures thereof. Currently, the preferred solvent is water alone, or a combination of water and any of the above as an auxiliary solvent.

[0027] The contact step of the present invention is typically performed at a temperature of about 0 to about 100°C, for example, about 10 to about 80°C, preferably about 20 to about 60°C. The process may be performed at a pressure below atmospheric pressure, atmospheric pressure, or above atmospheric pressure, preferably at atmospheric pressure or above atmospheric pressure. Suitable pressures include 0 bar to about 30 bar, for example, about 0.5 bar to about 20 bar, preferably about 1 to about 5 or about 10 bar.

[0028] The composition is typically contacted with a basic solution containing a hydroxide, alkoxide and / or amide for about 1 second to about 4 hours, preferably about 10 seconds to about 3 hours, e.g., about 1 minute to about 180 minutes, preferably about 2 to about 100 minutes, about 5 to about 80 minutes, or about 10 to about 60 minutes (e.g., about 15 to about 45 minutes). This so-called residence time has proven to be an important parameter in the process of the present invention, along with other variables such as the temperature of the contact step and the concentration of the basic solution containing the hydroxide, alkoxide and / or amide (see below in this specification).

[0029] (Hydro)halocarbon and chemical formula R f A composition containing a compound of -C≡CX may be in a liquid or gaseous phase (preferably, gaseous phase) when in contact with a basic solution containing a hydroxide, an alkoxide and / or amide.

[0030] Before contacting with a basic solution containing a hydroxide, an alkoxide and / or amide, the composition preferably contains at least about 90 weight% of (hydro)halocarbons, for example, at least about 95 weight%, 98 weight%, 99 weight%, or 99.5 weight% of (hydro)halocarbons.

[0031] Before contact with a basic solution containing a hydroxide and / or amide, the composition typically contains R of about 10,000 ppm or less, for example, 5,000 ppm or less. f It includes a -C≡CX compound. Preferably, the composition contains, before contact with a basic solution containing a hydroxide, alkoxide and / or amide, an R of less than about 4000 ppm, 3000 ppm, 2000 ppm, 1000 ppm, 800 ppm, 700 ppm, 600 ppm, or 500 ppm or less. f It includes compounds of -C≡CX.

[0032] Formula R in a (hydro)halocarbon-containing composition f The amount of the compound of -C≡CX is typically reduced in the process of the present invention to at least about 20 weight% of the composition, preferably at least about 50 weight%, 60 weight%, 70 weight%, 80 weight%, 90 weight%, or 95 weight% or more of the composition.

[0033] After contact with a basic solution containing a hydroxide, alkoxide and / or amide, the composition typically contains 0 to about 1000 ppm, for example, 0 to about 500 ppm of formula R f It includes a compound of -C≡CX. Preferably, the composition comprises, after contact with a basic solution containing a hydroxide, an alkoxide and / or amide, a chemical formula R of less than about 400 ppm, 300 ppm, 200 ppm, 100 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm, or 5 ppm or less. f It includes compounds of -C≡CX.

[0034] In one embodiment, the contact step is performed in the presence of a phase transition catalyst. As used herein, the term “phase transition catalyst” means a substance that promotes the transition of a chemical compound from one phase to another. The phase transition catalyst may be ionic or neutral and is typically selected from the group consisting of crown ethers, onium salts, cryptands, polyalkylene glycols, and derivatives thereof (e.g., fluorinated derivatives thereof).

[0035] Typically, the amount of catalyst used is about 0.001 to about 20 weight% of the composition, for example, about 0.01 to about 10 weight%, for example, about 0.5 to about 5 weight%.

[0036] Crown ethers are cyclic molecules in which ether groups are linked by dimethylene linkages. Useful crown ethers include 18-crown-6, 15-crown-5, and 12-crown-4. Derivatives of the above crown ethers, for example, dibenzyl-18-crown-6, dicyclohexanyl-18-crown-6, dibenzyl-24-crown-8, and dibenzyl-12-crown-4 are also useful. Other compounds similar to crown ethers and useful for the same purpose are compounds that differ by the substitution of one or more oxygen atoms by different classes of donor atoms, in particular, N or S. Fluorinated derivatives of all the above may also be used.

[0037] Cryptons are another class of compounds useful as phase transition catalysts in base-mediated dehydrohalogenation. These are three-dimensional polymacrocyclic chelating agents formed by combining a chain containing appropriately spaced donor atoms with a bridgehead structure. The donor atoms of the bridge can all be O, N, or S, or the compound can be a mixed donor macrocycle in which the bridge strands contain a combination of these donor atoms. Suitable cryptons include a bicyclic molecule obtained from the combination of a chain of (-OCH2CH2-) groups and a nitrogen bridgehead, as in [2.2.2]cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosan, available under the trademarks Kryptand 222 and Kryptofix 222).

[0038] Onium salts that can be used as catalysts in base-mediated dehydrohalogenation processes include quaternary phosphonium salts and quaternary ammonium salts, which are each with the chemical formula R 1 R 2 R 3 R 4 P + Z - and R 1 R 2 R 3 R 4 N + Z - It can be expressed as. In this chemical formula, R 1 , R 2 , R 3 and R 4 Each typically, independently, C 1-10 alkyl groups, aryl groups (e.g., phenyl, naphthyl, or pyridinyl) or arylalkyl groups (e.g., benzyl or C 1-10 Representing an alkyl-substituted phenyl), and Z - is a halide or other suitable counterion (e.g., hydrogen sulfate).

[0039] Specific examples of these phosphonium salts and quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltrioctylammonium chloride (commercially available under the trademarks Aliquat 336 and Adogen 464), tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, and triphenylmethylphosphonium chloride. Benzyltriethylammonium chloride is preferred for use under strongly basic conditions. Quaternary ammonium chloride salts are a preferred class of onium salts for use as phase transition catalysts, e.g., Aliquat 336.

[0040] Other useful onium salts include onium salts that exhibit high temperature stability (e.g., up to about 200°C), e.g., 4-dialkylaminopyridinium salt, tetraphenylarsonium chloride, bis[tris(dimethylamino)phosphine]iminium chloride, and tetrakis[tris(dimethylamino)phosphineimino]phosphonium chloride.

[0041] Polyalkylene glycol compounds useful as phase transition catalysts have the chemical formula R 6 0(R 5 0) m R 7 It can be expressed as, and in the above equation, R 5 is C 1-10 It is an alkylene group, and each R 6 and R 7 is independently, H, C 1-10 alkyl groups, aryl groups (e.g., phenyl, naphthyl, or pyridinyl) or arylalkyl groups (e.g., benzyl or C 1-10 It is an alkyl-substituted phenyl), and m is an integer of at least 2. Preferably, R 6 and R 7Both are identical, and for example, both of these can be H.

[0042] These polyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, diisopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and tetramethylene glycol, monoalkyl glycol ethers, e.g., monomethyl, monoethyl, monopropyl and monobutyl ethers of these glycols, dialkyl ethers, e.g., tetraethylene glycol dimethyl ether and pentaethylene glycol dimethyl ether, phenyl ethers and benzyl ethers of these glycols, and polyalkylene glycols, e.g., polyethylene glycol (average molecular weight about 300) and polyethylene glycol (average molecular weight about 400) and dialkyl (e.g., dimethyl, dipropyl, dibutyl) ethers of these polyalkylene glycols.

[0043] Combinations of phase transition catalysts from one of the aforementioned groups, as well as combinations or mixtures from more than one group, may also be useful.

[0044] In one embodiment, (hydro)halocarbon and formula R f A composition comprising a compound of -C≡CX may be a product stream from a process for producing (hydro)halocarbons. Accordingly, the composition typically contains a target or desired (hydro)halocarbon, e.g., a hydrohalopropene (e.g., tetrafluoropropene, e.g., HFO-1234yf or HFO-1234ze, and / or chlorotrifluoropropene, e.g., HCFO-1233zd or HCFO-1233xf) and one or more (undesired) (hydro)halocarbon byproducts. The process may be carried out as a batch reaction, as a continuous reaction, or as a semi-continuous reaction.

[0045] Examples of such (hydro)halocarbon byproducts in a process for producing tetrafluoropropene (e.g., HFO-1234yf) and / or chlorotrifluoropropene (e.g., HCFO-1233xf) include pentafluoropropene (e.g., CF3CFH=CFH, HFO-1225ye), pentafluoropropane (e.g., HFC-245eb and / or HFC-245fa and / or HFC-245cb), chlorotetrafluoropropane (e.g., HCFC-244bb), and hexafluoropropane (e.g., CF3CFHCF2H, HFC-236ea).

[0046] Unexpectedly, the contact step of the present invention is formula R f Not only is it effective in reducing the concentration of -C=CX compounds, but also targets (hydro)halocarbons, chemical formula R f It has been confirmed that it can be effective in reducing the concentration of one or more by-products present in a composition containing a compound of -C=CX and (hydro)halocarbon by-products. This results in an increase in selectivity and / or yield for the desired (hydro)halocarbon. Preferably, the concentration of any saturated (hydro)halocarbon by-product is reduced for the desired (hydro)halocarbon.

[0047] In the desired (hydro)halocarbon-containing composition, the amount of (hydro)halocarbon byproduct is typically reduced to at least about 20 weight% of the composition in the process of the present invention, preferably at least about 50 weight%, 60 weight%, 70 weight%, 80 weight%, 90 weight%, or 95 weight% or more of the composition.

[0048] After contacting with a basic solution containing a hydroxide, an alkoxide and / or amide, the composition typically contains a compound of (hydro)halocarbon byproducts in an amount of 0 to about 1000 ppm, for example, 0 to about 500 ppm. Preferably, after contacting with a basic solution containing a hydroxide, an alkoxide and / or amide, the composition contains (hydro)halocarbon byproducts in an amount of less than about 400 ppm, 300 ppm, 200 ppm, 100 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm, or 5 ppm or less.

[0049] In a second aspect of the present invention, a process for producing (hydro)halocarbons is provided, comprising the following steps:

[0050] (i) starting materials, optionally, in the presence of HF and / or a catalyst, (hydro)halocarbons and formula R f -Compound of C≡CX (wherein R in the above formula f A step of converting to a composition comprising (where is a perfluorinated alkyl group and X is H, F, Cl, Br, or I);

[0051] (ii) contact the composition with a basic solution containing a hydroxide, alkoxide and / or amide to form formula R f - A step of reducing the concentration of the compound of C≡CX; and

[0052] (iii) Step of recovering (hydro)halocarbons.

[0053] To eliminate any possibility of doubt, for example, (hydro)halocarbon and chemical formula R f The information described above in relation to the first embodiment of the invention, relating to a composition comprising a compound of -C≡CX and a contact step, is also applicable to the second embodiment of the invention. Further embodiments of the second embodiment of the invention are described below.

[0054] (Hydro)halocarbon and R of the starting material in step (i)f The conversion to -C=CX impurities preferably includes hydrogenation, dehydrohalogenation, isomerization, and / or fluorination reactions.

[0055] In one embodiment, (hydro)halocarbon and formula R f A composition containing a compound of -C≡CX is prepared by a hydrogenation reaction.

[0056] These hydrogenation reaction(s) can be carried out in a liquid phase or a vapor phase, preferably in a vapor phase, typically at a temperature of about -50 to about 275°C. A preferred temperature for liquid phase hydrogenation is about -50 to about 50°C, for example, about 15 to about 40°C. A preferred temperature for vapor phase hydrogenation is about 0 to about 250°C, for example, about 20 to about 200°C, for example, about 50 to about 150°C.

[0057] Hydrogenation reaction(s) can be carried out, particularly when performed in a liquid phase, in the presence of a fluorinated polar aprotic solvent. Suitable solvents include HFCs (e.g., 134a) and PFCs (e.g., perfluorodecalin).

[0058] The hydrogenation reaction(s) may be carried out at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure, preferably above atmospheric pressure. For example, hydrogenation may be carried out at a pressure of about 0 to about 40 bara, for example, about 1 to about 30 bara, for example, about 5 to about 20 bara.

[0059] The ratio of hydrogen to reagent is suitably about 0.1:1 to about 40:1, for example, about 1:1 to about 20:1, preferably about 1.1:1 to about 10:1, for example, 1.5:1 to about 5:1.

[0060] Hydrogenation reaction(s) are typically carried out in the presence of a catalyst. Suitable hydrogenation catalysts include transition metals nickel (Ni), palladium (Pd), platinum (Pt), rhenium (Re), rhodium (Rh), ruthenium (Ru), and mixtures thereof. Such catalysts may be supported, for example, on alumina, titania, silica, zirconia, fluorides of the above, calcium fluoride, carbon, or barium sulfate, or may not be supported on such, and may be, for example, a Raney Ni or Pd metal formed by the reduction of PdO2. Examples of catalysts suitable for use in the present invention include Pd / alumina, Pd / barium sulfate, Pd / C, and chlorotris(triphenylphosphine)rhodium (I). Preferably, the catalyst is palladium (Pd / C) or chlorotris(triphenylphosphine)rhodium (I) (Wilkinson catalyst) supported on carbon or platinum (Pt / Al2O3) or Adams catalyst supported on alumina, in a form reduced in situ to PtO2, platinum metal. When Pd / C is used as a catalyst, Pd is present in an amount of about 0.01 to about 10 weight percent of the catalyst, for example, about 0.1 to about 5 weight percent.

[0061] The hydrogenation catalyst is typically used in an amount of about 0.01 to about 30 weight%, for example, about 0.1 to about 10 weight%, based on the total weight of the components constituting step (a) and step (c). When Pd / C is used as a catalyst, Pd is present in an amount of about 0.01 to about 10 weight% of the catalyst, for example, about 0.1 to about 5 weight%.

[0062] In the vapor phase, the contact time with the catalyst may be about 1 to about 200 seconds, for example, about 2 to about 150 seconds. In the liquid phase, the contact time with the catalyst is suitably about 1 to about 180 minutes, for example, about 2 to about 60 minutes.

[0063] In one embodiment, (hydro)halocarbon and formula R f A composition containing a compound of -C≡CX is prepared by a dehydrohalogenation reaction.

[0064] The dehydrohalogenation reaction involves (hydro)halocarbons and chemical formula R f This can be carried out by pyrolyzing a starting material to form a composition containing a compound of -C=CX. As used herein, the terms "pyrolyzing" or "pyrolysis" include the meaning of a chemical change formed by heating in the absence of a catalyst. The absence of a catalyst includes the meaning that no material or treatment is added to the pyrolysis reactor, thereby increasing the reaction rate by reducing the activation energy of the pyrolysis process.

[0065] For pyrolysis, any suitable reactor, for example, a cylindrical tube that is either straight or coiled, may be used. A preferred pyrolysis reactor comprises a reactor that partially obstructs the flow of gases through the reactor to induce reverse mixing, i.e., turbulence, thereby enhancing the mixing of gases and good heat transfer. Such partial obstruction can be conveniently achieved by placing packing inside the reactor and filling its cross-section, or by using perforated baffles. The reactor packing may be particulate or fibrillar, have an open structure similar to a Raschig ring, or have other packing with a large free volume to avoid cork accumulation and minimize pressure drop, generally enabling the free flow of gases. In some embodiments of the present invention, the reactor packing incorporates a cartridge for ease of insertion and removal. In some embodiments of the present invention, the pyrolysis reactor is substantially empty, meaning that the free volume of the reaction zone (the volume of the reaction zone minus the volume of the material constituting the reactor packing) is at least about 80%, preferably at least about 90%, and more preferably at least about 95%. In some embodiments, the pyrolysis reactor is made of a corrosion-resistant material comprising stainless steel, Hastelloy®, Inconel®, Monel®, gold, or gold-lined or quartz.

[0066] The dehydrohalogenation reaction of step (i) preferably comprises a dehydrofluorination process and / or dehydrochlorination depending on the starting material and the corresponding (hydro)halocarbon product. The pyrolysis temperature for dehydrofluorination is typically higher than that for dehydrochlorination. For example, dehydrofluorination pyrolysis can be carried out at a temperature of about 600°C to about 900°C, and dehydrochlorination pyrolysis can be carried out at a temperature of about 400°C to about 700°C.

[0067] In one embodiment, the dehydrohalogenation reaction is catalyzed. This reaction may be carried out in a liquid phase or a vapor phase, preferably in a vapor phase. A temperature of about -25 to about 700°C may be used. A preferred temperature for the liquid phase is about 0 to about 180°C, for example, about 15 to about 120°C. A preferred temperature for vapor phase dehydrohalogenation is about 100 to about 650°C, for example, about 200 to about 600°C, for example, about 300 to about 500°C.

[0068] The catalyzed dehydrohalogenation reaction may be carried out at atmospheric pressure, a pressure below atmospheric pressure, or a pressure above atmospheric pressure, preferably at atmospheric pressure or above atmospheric pressure. For example, dehydrohalogenation may be carried out at a pressure of about 0 to about 40 bara, for example, about 1 to about 30 bara, for example, about 1 or 5 to about 20 bara.

[0069] Preferably, the catalyst is stable in the presence of HF and / or HCl. Suitable catalysts include metal and carbon-based catalysts, e.g., activated carbon (including acid-washed carbon, activated carbon, and three-dimensional matrix carbonaceous materials), main group catalysts (e.g., alumina-based catalysts), and transition metal catalysts, e.g., chromia-based catalysts (e.g., zinc / chromia) or nickel-based catalysts (e.g., nickel mesh). Examples of such catalysts include alumina, fluorinated alumina, aluminum fluoride, aluminum chlorofluoride; metal compounds supported on alumina, fluorinated alumina, aluminum fluoride, or aluminum chlorofluoride; chromium oxide (Cr2O3), fluorinated chromium oxide, and cubic chromium trifluoride; oxides, fluorides, and oxyfluorides of magnesium, zinc, mixtures of magnesium and zinc, and / or aluminum. The composition comprises lanthanum oxide and fluorinated lanthanum oxide; carbon, and a metal compound supported on the carbon. The metal compound may be an oxide, fluoride, and oxyfluoride of at least one metal selected from the group consisting of sodium, potassium, rubidium, cesium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, chromium, iron, cobalt, rhodium, nickel, copper, zinc, and mixtures thereof. In some embodiments of the present invention, the dehydrohalogenation catalyst comprises an alkali metal salt supported on chromium oxide.

[0070] The catalyst used can be used in an amount of about 0.01 to about 50 weight%, for example, about 0.1 to about 30 weight%, for example, about 0.5 to about 20 weight% based on the weight of the reagent. The contact time with the catalyst in the catalyzed reaction is suitably about 1 to about 500 seconds, for example, about 5 to about 400 seconds.

[0071] Dehydrohalogenation can be carried out in any suitable equipment, e.g., a static mixer, a stirred tank reactor, or a stirred vapor-liquid separation vessel. Preferably, the equipment is made of one or more corrosion-resistant materials, e.g., Hastelloy® or Inconel®. The process can be carried out in batch or (semi-)continuously, preferably (semi-)continuously.

[0072] In one embodiment, (hydro)halocarbon and formula R f Compositions comprising compounds of -C≡CX are prepared by isomerization reactions. Suitable reaction conditions and catalysts include those described above for dehydrohalogenation reactions at somewhat lower temperatures, optionally. Suitable conditions for isomerization reactions are described, for example, in WO 2008 / 125825 and WO 2015 / 059500. The term "isomerization reaction" includes structural and geometric isomerization, such as the structural isomerization of CF2CH=CF2(HFO-1234zc) to HFO-1234ze and the geometric isomerization of Z-HFO-1234ze to E-HFO-1234ze.

[0073] In some embodiments, (hydro)halocarbon and formula R f A composition comprising a compound of -C≡CX is prepared by a fluorination reaction. Suitable reaction conditions and catalysts include those described above for the dehydrohalogenation reaction, except in the presence of a fluorination agent such as HF. Typically, HF is used in a molar excess relative to the starting material, e.g., about 1:1 to about 70:1, preferably about 2:1 to about 60:1, e.g., about 3:1 to about 50:1, e.g., about 5:1 to about 40:1. Suitable conditions for the fluorination reaction are described, for example, in EP-A-2154122 and WO 2011 / 077394.

[0074] The (hydro)halocarbon formed in step (i) is C3-7 (Hydro)haloalkenes, preferably hydrohalopropene, e.g., chlorotrifluoropropene and / or tetrafluoropropene.

[0075] Preferably, the starting material comprises one or more of CCl3CH2CCl2H(HFC-240fa), CF3CH2CFClH(HCFC-244fa), CF3CH2CF2H(HFC-245fa), CF3CF2CH3(HFC-245cb), CF3CFHCFH2(HFC-245eb), CF3CFClCH3(HCFC-244bb), HCFO-1233xf, tetrachloropropene (HCO-1230), Z-HFO-1234ze, Z-HCFO-1233zd, HFO-1234zc, and CCl3CClHCClH2(HFC-240db). The starting material may also be CF3CHClCH2Cl(HCFC-243db).

[0076] Advantageously, the hydrohalopropene is HCFO-1233zd and / or HFO-1234ze, wherein the starting material comprises one or more of CCl3CH2CCl2H (HFC-240fa), CF3CH2CFClH (HCFC-244fa), and CF3CH2CF2H (HFC-245fa), as described, for example, in US 2014 / 228600, which is incorporated herein by reference. In further embodiments, the hydrohalopropene may be E-HCFO-1233zd, wherein the starting material comprises E-HCFO-1233zd, or the hydrohalopropene may be E-HFO-1234ze, wherein the starting material comprises one or more of Z-HFO-1234ze or HFO-1234zc.

[0077] Preferably, the hydroxyhalopropene is HFO-1234yf, and the starting material comprises one or more of CF3CF2CH3 (HFC-245cb), CF3CFHCFH2 (HFC-245eb), CF3CFClCH3 (HCFC-244bb), HCFO-1233xf, tetrachloropropene (HCO-1230), and CCl3CClHCClH2 (HFC-240db) as described in WO 2008 / 04096 and WO 2010 / 123154, which are incorporated herein by reference. The starting material for preparing HFP-1234yf may also be CF3CHClCH2Cl (HCFC-243db).

[0078] Advantageously, the hydroxyhalopropene is HCFO-1233xf, and the starting materials comprise tetrachloropropene (HCO-1230) and / or CCl3CClHCClH2 (HFC-240db) as described in WO 2011 / 077394, which is incorporated herein by reference.

[0079] Preferably, the (hydro)halocarbon is HCFC-244bb, and the starting materials comprise one or more of HCFO-1233xf, tetrachloropropene (HCO-1230), and CCl3CClHCClH2 (HFC-240db), as described in WO 2007 / 125199, which are incorporated herein by reference.

[0080] In some embodiments of the present invention, (hydro)halocarbon and R f A composition comprising a compound of -C≡CX is mixed with a basic solution comprising a hydroxide, alkoxide, and / or amide in a vessel equipped with a stirrer, optionally, in the presence of a suitable solvent. For example, R fA (hydro)halocarbon containing -C≡CX impurities may be brought into contact with a basic solution containing hydroxide, alkoxide, and / or amide under a suitable amount of pressure to maintain the liquid phase (hydro)halocarbon and the basic solution containing hydroxide, alkoxide, and / or amide in a container. The contents of the contact container may be stirred to provide contact between the hydro)halocarbon and the basic solution containing hydroxide, alkoxide, and / or amide.

[0081] In some embodiments, the contact step is with (hydro)halocarbon and R f This can be carried out by contacting a gaseous mixture of -C≡CX impurities with a basic solution containing a hydroxide, alkoxide, and / or amide. For example, (hydro)halocarbons and R f A mixture containing C≡CX impurities may be bubbled as a gas into a basic solution containing a hydroxide, alkoxide, and / or amide in a stirred vessel. The (hydro)halocarbon may then, optionally, remain in a contact vessel through a condenser, whereby it may be further purified or recovered.

[0082] In some embodiments, the contact step is performed with a column packed in a material such as a spiral, ring, saddle, or other molded shape made of glass, plastic, or ceramic. (Hydro)halocarbon and R f A mixture containing -C≡CX impurities enters the bottom of the column as vapor. A basic solution containing hydroxides, alkoxides, and / or amides enters the top of the column, for example, using a pump connected to a reservoir of said basic solution containing hydroxides, alkoxides, and / or amides. R in (hydro)halocarbons f -C≡CX impurities are subsequently removed by contacting a basic solution containing hydroxides, alkoxides, and / or amides in the column, and the reduced R f(Hydro)halocarbon vapors containing -C≡CX impurities proceed out of the top of the column and are subsequently collected. Basic solutions containing hydroxides, alkoxides and / or amides proceed out of the bottom of the column and are returned to the reservoir.

[0083] The (hydro)halocarbon is recovered in step (iii) by any suitable means, for example, including distillation and / or phase separation.

[0084] The process of the present invention may include one or more additional purification steps, e.g., distillation, condensation, scrubbing, phase separation, acid removal, polishing, and / or drying.

[0085] HF and optionally HCl may be present in the composition formed from the conversion step. Preferably, at least some of the HF in the composition, and optionally, HCl, are removed prior to the contact step. The acid may be removed, for example, by flash separation, aqueous scrubbing, and / or distillation. If bulk removal of HF occurs prior to the contact step (ii), residual HF (and optionally, HCl) is advantageously removed by the contact step.

[0086] If the basic solution containing the hydroxide, alkoxide and / or amide used in step (ii) is aqueous, it is preferable to have a drying step. Drying of the (hydro)halocarbon can be achieved by known methods, e.g., treatment with sulfuric acid and / or contact with a porous medium, e.g., silica, an aluminum-containing adsorbent (e.g., zeolite), or activated carbon.

[0087] As understood by those skilled in the art, any preferred and alternative embodiments presented above may be applied to any described aspect of the present invention. Specific details for implementing the invention

[0088] The present invention is illustrated by the following non-limiting embodiments.

[0089] Examples

[0090] Experiment Department

[0091] A feed mixture was prepared by adding TFMA (2.5 g) to HFO-1234yf (499.98 g). This mixture containing 0.50 wt% TFMA was used for all experiments.

[0092] A solid base was accurately weighed into a 100 ml Hastelloy C22 autoclave and dissolved in a known weight of deionized water. If used, a phase transition catalyst was also added at this time. The vessel was sealed, purged with nitrogen, and evacuated. It was subsequently pressurized with an HFO-1234yf / TFMA feed mixture (4 to 4.5 Barg). The contents of the vessel were then stirred at 1000 rpm and heated to a desired temperature over a period of 4 to 5 minutes. Once the desired temperature was reached, a sample of the gas in the upper space of the vessel was periodically ejected and analyzed by gas chromatography.

[0093] result

[0094] Experiments were performed using various basic reagents at different concentrations, temperatures, and both in the presence and absence of a phase transition catalyst (Aliquat 336). The results are described in Tables 1 through 8.

[0095] Table 1 (Example 1)

[0096]

[0097] Table 2 (Example 2)

[0098]

[0099] Table 3 (Example 3)

[0100]

[0101] Table 4 (Example 4)

[0102]

[0103] Table 5 (Example 5)

[0104]

[0105] Table 6 (Example 6)

[0106]

[0107] Table 7 (Example 7)

[0108]

[0109] Table 8 (Example 8)

[0110]

[0111] It can be seen that treatment with a base is very effective in reducing the absolute concentration of TFMA in the mixture and increasing the HFO-1234yf content of the mixture relative to the total TFMA.

[0112] A reduction in other trace impurities was also observed after treatment with a base, and the results of reducing other impurities are summarized in Tables 9 and 10.

[0113] Table 9 (Example 9)

[0114]

[0115] Table 10 (Example 10)

[0116]

[0117] Accordingly, the process of the present invention is also effective in reducing the levels of R-1225ye(Z), R-236ea, and R-245eb in a composition containing HFO-1234yf.

[0118] Experiment Department

[0119] A feed mixture was prepared by adding TFMA (1.25 g) to HFO (250 g). This mixture containing 0.50 wt% TFMA was used for all experiments.

[0120] In a typical scrubbing experiment, the base was accurately weighed into a 100 ml Hastelloy C22 autoclave and dissolved in a known weight of deionized water or solvent. If used, any additional additives, e.g., KF or a catalyst, were also added at this time. The vessel was subsequently sealed, purged with nitrogen, evacuated, and heated to the desired temperature over 5 minutes. Once such a temperature was reached, the vessel was subsequently pressurized with an HFO / TFMA feed mixture. The contents of the vessel were subsequently stirred at 1000 rpm, and a sample of the gas in the upper space of the vessel was periodically ejected and analyzed by gas chromatography.

[0121] result

[0122] Experiments were performed using various basic reagents and hydrofluoroolefins (HFO). The results are described in Tables 11 to 15.

[0123] Table 11 (Example 11 - Removal of TFMA from E-1234ze)

[0124]

[0125] Table 12 (Example 12 - Removal of TFMA from 1233xf*)

[0126]

[0127] * To aid in sampling, the container was first pressurized to 1.4 bar with a 1233xf mixture, and then to 5.4 bar with nitrogen.

[0128] Table 13 ( Examples 13 - Sodium in ethanol ethoxide From 1234yf TFMA eliminate)

[0129]

[0130] Table 14 (Example 14 - Removal of TFMA from E-1234yf in the presence of fluoride)

[0131]

[0132] Table 15 (Example 15 - Removal of TFMA from E-1234yf in the absence of fluoride)

[0133]

[0134] It can be seen that treatment with a base is very effective in reducing the absolute concentration of TFMA in a mixture of HFO and the base within a specified range and increasing the HFO content of the mixture relative to TFMA.

[0135] The present invention is defined by the claims.

Claims

Claim 1 As a method, chemical formula R f -C≡CX(where R f To reduce the concentration of (where is a perfluorinated alkyl group and X is H, F, Cl, Br, or I), (hydro)halocarbon and the above formula R f A method comprising the step of contacting a composition containing a compound of -C≡CX with a basic solution containing a hydroxide, an alkoxide and / or an amide, wherein the method further comprises the step of drying the (hydro)halocarbon. Claim 2 In claim 1, the (hydro)halocarbon is C 3-7 (Hydro)haloalkene, method. Claim 3 In paragraph 2, the above C 3-7 A method in which the (hydro)haloalkene is hydrohalopropene. Claim 4 A method according to paragraph 3, wherein the hydrohalopropene is chlorotrifluoropropene and / or tetrafluoropropene. Claim 5 A method according to claim 4, wherein the chlorotrifluoropropene is CF3CH=CHCl(HCFO-1233zd) and / or CF3CCl=CH2(HCFO-1233xf). Claim 6 In paragraph 4, the method wherein the tetrafluoropropene is CF3CH=CHF(HFO-1234ze) and / or CF3CF=CH2(HFO-1234yf). Claim 7 In claim 1, (hydro)halocarbon and chemical formula R f A method comprising: a composition containing a compound of -C≡CX, further comprising an undesired (hydro)halocarbon, and contacting the composition with a basic solution containing a hydroxide, an alkoxide and / or an amide to reduce the concentration of the undesired (hydro)halocarbon. Claim 8 A method according to claim 7, wherein the undesired (hydro)halocarbon is selected from pentafluoropropene, pentafluoropropane, chlorotetrafluoropropane, hexafluoropropane, and mixtures thereof. Claim 9 A method according to claim 8, wherein the above-mentioned undesired (hydro)halocarbon is one or more of CF3CFH=CFH(HFO-1225ye), HFC-245eb, HFC-245fa, HFC-245cb, HCFC-244bb and HFC-236ea. Claim 10 A method according to any one of claims 7 to 9, wherein the amount of the undesirable (hydro)halocarbon in the composition is reduced by at least 50 weight%. Claim 11 A method according to claim 10, wherein the amount of the undesired (hydro)halocarbon in the composition is reduced by at least 70 weight percent. Claim 12 A method according to claim 11, wherein the amount of the undesirable (hydro)halocarbon in the composition is reduced by at least 90 weight percent. Claim 13 A method according to any one of claims 7 to 9, wherein, after the contacting step, the obtained composition contains 0 to 500 ppm of the undesired (hydro)halocarbon compound. Claim 14 A method according to claim 13, wherein, after the contacting step, the obtained composition contains 0 to 100 ppm of the undesired (hydro)halocarbon compound. Claim 15 A method according to claim 14, wherein, after the contacting step, the obtained composition contains 0 to 10 ppm of the undesired (hydro)halocarbon compound. Claim 16 A method according to claim 1, wherein the composition is a product stream from a method for producing the (hydro)halocarbon. Claim 17 A method in paragraph 16 that is combined with one or more additional purification steps. Claim 18 A method for preparing a (hydro)halocarbon, comprising: (i) starting materials of a (hydro)halocarbon and formula R f -Compound of C≡CX (wherein R in the above formula f (ii) converting to a composition comprising (where is a perfluorinated alkyl group and X is H, F, Cl, Br, or I); (ii) the formula R f A method comprising the steps of: contacting the composition with a basic solution containing a hydroxide, an alkoxide and / or an amide to reduce the concentration of the compound of -C≡CX; and (iii) recovering the (hydro)halocarbon. Claim 19 In paragraph 18, the method wherein step (i) is performed in the presence of HF and / or a catalyst. Claim 20 In claim 1 or claim 18, the above formula R f - A method in which the compound of -C≡CX is 3,3,3-trifluoropropine (trifluoromethylacetylene, TFMA). Claim 21 A method according to claim 1 or 18, wherein the solution is an aqueous solution. Claim 22 In claim 1 or 18, the solution is an alkali metal hydroxide, alkoxide or amide, an alkaline earth metal hydroxide or amide, or NR4OH (wherein R is independently H, C 1-10 alkyl, aryl A method comprising one or more of the arylalkyl groups. Claim 23 In claim 22, the method wherein the aryl group is selected from the group consisting of phenyl, naphthyl, and pyridinyl. Claim 24 In Clause 22, the arylalkyl group is benzyl and C 1-10 A method selected from the group consisting of alkyl-substituted phenyls. Claim 25 A method according to claim 22, wherein the solution contains one or more of potassium hydroxide (KOH), sodium hydroxide (NaOH), or calcium hydroxide (Ca(OH)2). Claim 26 A method according to claim 1 or 18, wherein the solution has a concentration of 0.1 to 10 M. Claim 27 In claim 26, the method wherein the solution has a concentration of 0.2 to 5 M. Claim 28 In claim 27, the method wherein the solution has a concentration of 0.5 to 3 M. Claim 29 In paragraph 18, the above (hydro)halocarbon is C 3-7 (Hydro)haloalkene, method. Claim 30 In Clause 29, the above C 3-7 A method in which the (hydro)haloalkene is hydrohalopropene. Claim 31 In claim 30, the method wherein the hydrohalopropene is chlorotrifluoropropene and / or tetrafluoropropene. Claim 32 A method according to claim 31, wherein the starting material comprises one or more of CCl3CH2CCl2H(HFC-240fa), CF3CH2CFClH(HCFC-244fa), CF3CH2CF2H(HFC-245fa), CF3CF2CH3(HFC-245cb), CF3CFHCFH2(HFC-245eb), CF3CFClCH3(HCFC-244bb), CF3CHClCH2Cl(HCFC-243db), HCFO-1233xf, tetrachloropropene (HCO-1230), Z-HFO-1234ze, Z-HCFO-1233zd, HFO-1234zc, or CCl3CClHCClH2(HFC-240db). Claim 33 The method of claim 31, wherein the hydrohalopropene is HCFO-1233zd and / or HFO-1234ze, and the starting material comprises one or more of CCl3CH2CCl2H (HFC-240fa), CF3CH2CFClH (HCFC-244fa), or CF3CH2CF2H (HFC-245fa). Claim 34 A method according to claim 31, wherein the hydrohalopropene is HFO-1234yf and the starting material comprises one or more of CF3CF2CH3(HFC-245cb), CF3CFHCFH2(HFC-245eb), CF3CFClCH3(HCFC-244bb), CF3CHClCH2Cl(HCFC-243db), HCFO-1233xf, tetrachloropropene (HCO-1230), or CCl3CClHCClH2(HFC-240db). Claim 35 A method according to claim 31, wherein the hydroxyhalopropene is HCFO-1233xf and the starting material comprises tetrachloropropene (HCO-1230) and / or CCl3CClHCClH2 (HFC-240db). Claim 36 A method according to claim 31, wherein the (hydro)halocarbon is HCFC-244bb and the starting material comprises one or more of HCFO-1233xf, tetrachloropropene (HCO-1230) or CCl3CClHCClH2 (HFC-240db). Claim 37 A method according to claim 1 or 18, wherein the contacting step is performed in the presence of a phase transition catalyst. Claim 38 A method according to claim 1 or 18, wherein the contacting step is performed at a temperature of 0 to 100°C. Claim 39 A method according to claim 38, wherein the contacting step is performed at a temperature of 10 to 80°C. Claim 40 A method according to claim 39, wherein the contacting step is performed at a temperature of 20 to 60°C. Claim 41 A method according to claim 1 or 18, wherein the contacting step has a contact time between the composition and the solution of 1 second to 4 hours. Claim 42 A method according to claim 41, wherein the contacting step has a contact time between the composition and the solution of 10 seconds to 3 hours. Claim 43 A method according to claim 42, wherein the contacting step has a contact time between the composition and the solution of 1 minute to 180 minutes. Claim 44 A method according to claim 1 or 18, wherein the composition is in a gaseous phase at least before contact with the solution. Claim 45 A method according to claim 1 or 18, wherein the composition comprises at least 90 weight percent (hydro)halocarbon prior to the contacting step. Claim 46 A method according to claim 45, wherein the composition comprises at least 95 weight% of (hydro)halocarbon prior to the contacting step. Claim 47 In claim 1 or 18, the composition is 10,000 ppm or less of the formula R before the contacting step. f A method containing a compound of -C≡CX. Claim 48 In claim 47, the composition, prior to the contacting step, contains 5000 ppm or less of the formula R. f A method containing a compound of -C≡CX. Claim 49 In claim 48, the composition, prior to the contacting step, contains 1000 ppm or less of the formula R. f A method containing a compound of -C≡CX. Claim 50 In claim 1 or 18, the formula R in the composition f A method in which the amount of the compound of -C≡CX is reduced by at least 50 weight% in the contacting step. Claim 51 In claim 50, the above formula R in the above composition f A method in which the amount of the compound of -C≡CX is reduced by at least 70 weight% in the contacting step. Claim 52 In claim 51, the formula R in the above composition f A method in which the amount of the compound of -C≡CX is reduced by at least 90 weight% in the contacting step. Claim 53 In claim 1 or 18, after the contacting step, the obtained composition has 0 to 500 ppm of the formula R f A method containing a compound of -C≡CX. Claim 54 In claim 53, after the contacting step, the obtained composition has 0 to 100 ppm of the formula R. f A method containing a compound of -C≡CX. Claim 55 In claim 54, after the contacting step, the obtained composition has 0 to 10 ppm of the formula R. f A method containing a compound of -C≡CX. Claim 56 A method according to claim 18, further comprising one or more additional purification steps. Claim 57 In claim 18, the method wherein HF is present in the composition obtained from the above-mentioned conversion step. Claim 58 A method according to claim 57, wherein at least a portion of the HF in the composition is removed before the contacting step. Claim 59 A method according to claim 1 or 18, wherein the drying step of the (hydro)halocarbon is performed by treatment with sulfuric acid and / or contact with a porous medium. Claim 60 In paragraph 59, the porous medium is selected from silica, an aluminum-containing adsorbent, or activated carbon. Claim 61 In paragraph 60, the method wherein the aluminum-containing adsorbent is a zeolite.

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