Dehydration method for fluorine-based hydrocarbon compound

Abstract

To provide a method for dehydrating a composition containing a fluorine-based hydrocarbon compound such as HFC-134a.SOLUTION: A dehydration method includes a step of bringing a composition containing a fluorine-based hydrocarbon compound into contact with zeolite.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for dehydrating fluorinated hydrocarbon compounds. [Background technology]

[0002] Fluorinated hydrocarbon compounds such as difluoromethane (HFC-32) are widely used as etching gases in semiconductor manufacturing processes.

[0003] Conventionally, fluorine-based hydrocarbon compounds such as HFC-32 have been treated with A-type zeolite to adsorb moisture. The resulting mixture is then dehydrated (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5446710 Summary of the Invention [Problem to be solved by the invention]

[0005] The present disclosure aims to provide a method for dehydrating a composition containing a fluorinated hydrocarbon compound such as HFC-134a. [Means for solving the problem]

[0006] The present disclosure encompasses the following configurations.

[0007] Section 1. A method for dehydrating a composition containing a fluorinated hydrocarbon compound, comprising: The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- at least one compound selected from the group consisting of tetrafluoropropene (HFO-1234yf), A dehydration method comprising the step of contacting a composition containing the fluorine-containing hydrocarbon compound with a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more.

[0008] Section 2. A method for dehydrating a composition containing a fluorinated hydrocarbon compound, comprising: The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- at least one compound selected from the group consisting of tetrafluoropropene (HFO-1234yf), The composition containing the fluorine-containing hydrocarbon compound is treated with a zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. A method for dehydration comprising contacting with at least one zeolite.

[0009] Section 3. 3. The dehydration method according to item 1 or 2, wherein the step reduces the water content of the composition after dehydration to less than 3 ppmwt.

[0010] Section 4. Furthermore, the composition containing the fluorine-containing hydrocarbon compound is contacted with the zeolite, Any of items 1 to 3 above, which includes a step of removing 1,2,2-tetrafluoroethane (HFC-134). The dehydration method according to claim 1.

[0011] The process preferably reduces the content of HFC-134 in the composition after dehydration to less than 3 ppmwt. This is a dehydration method.

[0012] The content (ppm) of HFC-134 can be determined by, for example, gas chromatography, mass spectrometry (GC / MS), and then NMR. When measuring by structural analysis using NMR spectroscopy, The content (volume) of HFC-134 in the composition containing the substance containing fluorinated hydrocarbon compounds It is the volume fraction divided by the volume of the composition, i.e. ppmvol (vol / vol).

[0013] The content (ppm) of HFC-134 can be expressed as, for example, less than 3 ppmvol.

[0014] Section 5. A method for producing a composition containing a fluorinated hydrocarbon compound, comprising: The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- at least one compound selected from the group consisting of tetrafluoropropene (HFO-1234yf), A production method comprising the step of contacting a composition containing the fluorine-containing hydrocarbon compound with a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more.

[0015] Section 6. A method for producing a composition containing a fluorinated hydrocarbon compound, comprising: The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- at least one compound selected from the group consisting of tetrafluoropropene (HFO-1234yf), The composition containing the fluorine-containing hydrocarbon compound is treated with a zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. A method of making the same, comprising the step of contacting with at least one zeolite.

[0016] Section 7. 7. The method according to item 5 or 6, wherein the composition after contacting with the zeolite has a water content of less than 3 ppmwt.

[0017] Section 8. 8. Any of items 5 to 7, further comprising a step of contacting the composition containing the fluorinated hydrocarbon compound with the zeolite to remove 1,1,2,2-tetrafluoroethane (HFC-134). The manufacturing method described in

[0018] After contacting the zeolite, the composition preferably contains less than 3 ppmwt of HFC-134. This is a manufacturing method that satisfies the above requirements.

[0019] Section 9. A zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more is mixed with a fluorocarbon selected from the group consisting of 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3-tetrafluoropropene (HFO-1234yf). a composition containing at least one fluorine-containing hydrocarbon compound, 1. A method for producing a high-purity fluorine-containing hydrocarbon compound, comprising a step of removing impurities contained in a hydrogen fluoride compound.

[0020] Section 10. At least one type of zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite is doped with 1,1,1,2-tetramethylbenzyl ether. Pentafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoroethane 1. A method for producing a high-purity fluorine-containing hydrocarbon compound, comprising the step of contacting a composition containing at least one fluorine-containing hydrocarbon compound selected from the group consisting of fluoromethane (HFC-32) and 2,3,3,3-tetrafluoropropene (HFO-1234yf) with a fluorine-containing hydrocarbon compound to remove impurities contained in the fluorine-containing hydrocarbon compound.

[0021] Section 11. The impurities are selected from the group consisting of water and 1,1,2,2-tetrafluoroethane (HFC-134). 11. The dehydration method according to item 9 or 10, wherein the component is at least one selected from the group consisting of:

[0022] Section 12. 12. The method according to any one of items 9 to 11, wherein the concentration of water contained in the fluorinated hydrocarbon compound after the impurity removal is less than 3 ppmwt. In this production method, the concentration of HFC-134 contained in the fluorinated hydrocarbon compound after the impurity removal is preferably less than 3 ppmwt.

[0023] Section 13. A composition comprising a fluorinated hydrocarbon compound, The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- tetrafluoropropene (HFO-1234yf), Compositions containing less than 3 ppmwt of water and / or less than 3 ppmwt of HFC-134 .

[0024] Section 14. Item 14. The composition according to item 13, which is used as an etching gas, a refrigerant, a heat transfer medium, a deposit gas, a building block for organic synthesis, or a cleaning gas. [Effects of the Invention]

[0025] According to the present disclosure, there is provided a method for dehydrating a composition containing a fluorinated hydrocarbon compound such as HFC-134a. DETAILED DESCRIPTION OF THE INVENTION

[0026] It is important to remove moisture from etching gases in semiconductor manufacturing processes.

[0027] As a result of intensive research, the present inventors have found that when dehydrating a composition containing a fluorinated hydrocarbon compound such as HFC-134a, by bringing the composition containing a fluorinated hydrocarbon compound such as HFC-134a into contact with a zeolite having a silica-alumina (SiO2 / Al2O3) ratio (molar ratio) of 5 or more, or by bringing the composition into contact with a chabazite-type zeolite, the water adsorbed in the zeolite is inhibited from being released from the zeolite even over the course of the dehydration treatment, and water is successfully removed (dehydrated) from the composition containing a fluorinated hydrocarbon compound such as HFC-134a.

[0028] The present disclosure was completed as a result of further research based on this finding.

[0029] The present disclosure includes the following embodiments.

[0030] (1) Method for dehydrating a composition containing a fluorinated hydrocarbon compound The method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure includes a step of contacting the composition containing a fluorinated hydrocarbon compound with a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more.

[0031] The method for dehydrating a composition containing a fluorine-containing hydrocarbon compound according to the present disclosure includes dehydrating a composition containing a fluorine-containing hydrocarbon compound with at least one zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. The method includes a step of contacting.

[0032] The method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure preferably further comprises the step of contacting the composition containing the fluorinated hydrocarbon compound with the zeolite to remove 1,1,2,2-tetrafluoroethane (HFC-134).

[0033] In the method for dehydrating a composition containing a fluorine-containing hydrocarbon compound according to the present disclosure, the fluorine-containing hydrocarbon compound is 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3-tetrafluoropropene. (HFO-1234yf) and at least one compound selected from the group consisting of:

[0034] In the present disclosure, the process is carried out so that the maximum water content of the composition after dehydration is 10 ppmwt (by mass). / mass), and the water content is preferably less than 3 ppmw. In the present disclosure, the minimum water content in the composition after dehydration is about 0.1 ppmwt.

[0035] In the present disclosure, the maximum content of HFC-134 in the composition after dehydration is about 10 ppmwt (mass / mass), and preferably the content of HFC-134 is less than 3 ppmwt. In the example, the minimum content of HFC-134 in the composition after dehydration is about 0.1 ppmwt.

[0036] In the present disclosure, the process more preferably results in a composition after dehydration having a water content of less than 3 ppmwt and an HFC-134 content of less than 3 ppmwt.

[0037] In the present disclosure, the content (ppm) of HFC-134 is measured, for example, by performing mass analysis by gas chromatography / mass spectrometry (GC / MS) using gas chromatography, followed by structural analysis by NMR spectroscopy. In this case, the content (volume) of HFC-134 contained in a composition containing a fluorinated hydrocarbon compound is determined by the mass of the fluorinated hydrocarbon compound. The volume fraction is expressed as a percentage of the total volume of the compound divided by the volume of the composition containing the compound, i.e., ppmvol (vol / vol).

[0038] The content (ppm) of HFC-134 can be expressed as, for example, less than 3 ppmvol.

[0039] The method for dehydrating a composition containing a fluorine-containing hydrocarbon compound according to the present disclosure uses a specific zeolite when dehydrating a fluorine-containing hydrocarbon compound such as HFC-134a. This method inhibits the release of moisture adsorbed by the zeolite over time, thereby providing the advantages of efficient removal of moisture from a composition containing a fluorine-containing hydrocarbon compound such as HFC-134a, and further, preferably efficient removal of HFC-134 from a composition containing a fluorine-containing hydrocarbon compound such as HFC-134a. This has the advantage that

[0040] (1-1) Composition containing a fluorinated hydrocarbon compound Fluorinated hydrocarbon compounds such as HFC-134a are used as etching gases for silicon oxide and related materials in the manufacturing of semiconductors. Fluorinated hydrocarbon compounds such as HFC-134a used in the semiconductor industry are required to be extremely pure. It is particularly important to remove moisture from etching gases in the semiconductor manufacturing process.

[0041] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the fluorinated hydrocarbon compound is at least one selected from the group consisting of HFC-134a, HFC-125, HFC-32, and HFO-1234yf. It contains at least one compound.

[0042] Compositions containing fluorinated hydrocarbon compounds such as HFC-134a contain impurities that are mixed in during the production of fluorinated hydrocarbon compounds such as HFC-134a. These impurities include intermediates, isomers, by-products (e.g., hydrogen fluoride, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, fluoroalkenes, etc.).

[0043] Furthermore, compositions containing fluorine-based hydrocarbon compounds such as HFC-134a contain impurities that are mixed in when the fluorine-based hydrocarbon compounds such as HFC-134a are used. When fluorine-based hydrocarbon compounds such as HFC-134a are used as etching gases for semiconductor manufacturing, the impurities include water, acids such as HF, fluorocarbons, non-condensable gases (N, CO, CO, CH, O), etc. When used as a refrigerant for a refrigerator, the impurity includes water.

[0044] Compositions containing fluorinated hydrocarbon compounds such as HFC-134a contain 1,1,2,2-tetrafluoroethane (HFC-134) as an impurity other than water.

[0045] The presence of impurities such as water or hydrogen fluoride in a composition containing a fluorinated hydrocarbon compound such as HFC-134a may cause alteration (decomposition, polymerization, isomerization, etc.) of the fluorinated compound, particularly if the fluorinated compound is chemically unstable due to the presence of reactive sites such as double bonds, resulting in a vicious cycle of further reduction in purity.

[0046] In the present disclosure, the impurities that are adsorbed and removed by zeolite include, in particular, those containing water, those containing hydrogen fluoride, those containing hydrocarbons, those containing halogenated carbon compounds, those containing halogenated hydrocarbon compounds (HFC-134, etc.), and those containing fluorinated hydrocarbons that are brought into contact with the zeolite. These include isomers of the compound, such as positional isomers of carbon-carbon double bonds, cyclic isomers, etc.

[0047] Specific examples of the impurities include heptafluorobutene, chloroheptafluorobutene, methyl iodide, and chlorotrifluoroethylene.

[0048] In the semiconductor industry, the removal of moisture is particularly important from compositions containing fluorinated hydrocarbon compounds such as HFC-134a.

[0049] (1-2) Zeolite The method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure comprises the step of contacting a composition containing a fluorinated hydrocarbon compound such as HFC-134a with a specific zeolite.

[0050] Zeolite is a type of clay mineral with regular channels (tubular pores) and It is a hydrous aluminosilicate containing alkali or alkaline earth metals, consisting of a rigid anionic framework with cavities.

[0051] Zeolites are generally (M I ,M II 1 / 2 ) m (Al m Si n O 2(m+n) )·xH2O, (n≧m) (M I :Li + , Na + , K. + et al., M. II :Ca 2+ , Mg 2+ , Ba 2+ etc.) where the cations compensate for the negative charge of the aluminosilicate framework.

[0052] There is no particular restriction on the type of cation in the zeolite. + , Li + , Na + , K. + , Ca 2+ , Mg 2+ , Ba 2+etc. are used.

[0053] The basic structural unit is a tetrahedron structure of SiO4 or AlO4 (collectively called a TO4 tetrahedron), which These are connected infinitely in three dimensions to form crystals. In zeolite, the crystals are porous. The diameter of the pores is usually about 0.2 nm to 1.0 nm (2 Å to 10 Å). Zeolite has a molecular sieve effect, meaning that molecules larger than the pore size of the zeolite cannot enter. Zeolite has a molecular sieve effect due to the pores derived from its framework structure. In addition, it has properties such as solid acidity, ion exchange capacity, catalytic capacity, and adsorption capacity.

[0054] In the present disclosure, bringing a composition containing a fluorinated hydrocarbon compound such as HFC-134a into contact with a specific zeolite means passing the fluorinated hydrocarbon compound such as HFC-134a through a column or the like packed with zeolite, or packing the fluorinated hydrocarbon compound such as HFC-134a into a container packed with zeolite.

[0055] In the present disclosure, the form of use of the zeolite is not particularly limited. A composition containing a fluorinated hydrocarbon compound such as HFC-134a may be circulated through an apparatus filled with zeolite, or a container filled with zeolite may be filled with a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and the dehydrated composition containing a fluorinated hydrocarbon compound such as HFC-134a may be withdrawn after a predetermined time has elapsed.

[0056] The method for dehydrating a composition containing a fluorine-based hydrocarbon compound according to the present disclosure includes the steps of contacting the composition containing a fluorine-based hydrocarbon compound with a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more as described below, or contacting the composition with at least one zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. The method includes a step of:

[0057] Silica-alumina ratio (SiO 2 / Al 2 O 3 Zeolite with a ratio of 5 or more In the present disclosure, a zeolite having a silica-alumina ratio (SiO2 / Al2O3 ratio) (molar ratio) of 5 or more is used because it can efficiently dehydrate a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and the release of water from the zeolite is effectively suppressed even after the elapse of the dehydration treatment time, and more preferably, it can efficiently remove HFC-134 from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. The SiO2 / Al2O3 ratio is preferably 5.5 or more, and more preferably 6 or more.

[0058] In the present disclosure, the SiO2 / Al2O3 ratio of the zeolite used is preferably 50 or less, more preferably It is preferably 45 or less, and more preferably 40 or less.

[0059] In the present disclosure, if the SiO2 / Al2O3 ratio is less than 5, the polarity of the zeolite becomes high, and if it is more than 50, the polarity of the zeolite becomes low, so it is preferable to use a zeolite with an SiO2 / Al2O3 ratio of 5 to 50.

[0060] In the present disclosure, if the SiO2 / Al2O3 ratio is less than 5, the polarity of the zeolite becomes high, and if the SiO2 / Al2O3 ratio is more than 50, the polarity of the zeolite becomes low. Therefore, it is preferable to use a zeolite with an SiO2 / Al2O3 ratio of 5 to 50.

[0061] (i) Chabazite-type zeolite The chabazite (CHA) structure has a three-dimensional pore structure with a pore diameter of approximately 0.38 nm (3.8 Å). ) and has a large cage inside.

[0062] In the present disclosure, chabazite-type (CHA-type) zeolite is used because it can efficiently dehydrate compositions containing fluorinated hydrocarbon compounds such as HFC-134a, and the release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time, and more preferably, it can efficiently remove HFC-134 from compositions containing fluorinated hydrocarbon compounds such as HFC-134a. In the present disclosure, a specific chabazite-type (CHA-type) zeolite is used among commercially available zeolites. Zeolites of the zeolite type can be used.

[0063] The chabazite genus includes glimmenite, erionite, rubinite, and chabazite types.

[0064] In the present disclosure, chabazite-type zeolite means a zeolite that is included in the chabazite genus, and preferably, a zeolite having at least one type selected from the group consisting of chabazite-type, glimmenite-type, erionite-type, and rubinite-type is preferably used. In the example shown, as the chabazite-type zeolite, more preferably, chabazite-type zeolite or a mixed zeolite (synthetic zeolite) containing chabazite-type and another chabazite-type such as glimmenite-type, erionite-type, or rubinite-type is used, and even more preferably, a mixed zeolite (synthetic zeolite) containing chabazite-type and another chabazite-type such as erionite-type is used.

[0065] Specifically, in the present disclosure, the crystalline system of the chabazite-type zeolite is a mixture of the natural minerals chabazite and erionite, that is, a chabazite-type synthetic zeolite ( A synthetic zeolite that is a mixture of chabazite-type zeolite and erionite-type synthetic zeolite is preferably used.

[0066] The silica / alumina ratio (SiO2 / Al2O3) of the natural mineral chabazite is generally around 2, but the silica / alumina ratio (SiO2 / Al2O3) of synthetic chabazite-type zeolite is 6.1 to 6.7. That's about it.

[0067] (ii) Mordenite-type zeolite Mordenite, also known as mordenite, has the chemical formula (Ca, K, Na) [AlSiO 12 〕2·7H2O and is a silicate mineral. Mordenite structure is Generally, the porous structure is composed of 12-membered and 8-membered oxygen rings in which SiO4 and AlO4 are bonded by sharing oxygen. It is a zeolite with a 12-membered oxygen ring of about 0.67 nm x 0.70 nm in pore size, and 8 oxygen atoms. The ring is approximately 0.29 nm x 0.57 nm.

[0068] In the present disclosure, a mordenite-type zeolite is used because it can efficiently dehydrate a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and the release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time, and more preferably because it can efficiently remove HFC-134 from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. Certain commercially available mordenite-type zeolites may be used in the present disclosure.

[0069] (iii) Beta zeolite Beta zeolite is a type of crystalline aluminosilicate containing Si and Al, and has a three-dimensional pore structure containing pores of 12-membered oxygen rings.

[0070] In the present disclosure, it is possible to efficiently dehydrate a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and the release of water from the zeolite is good even after the elapse of the dehydration treatment time. Beta zeolite is preferably used in view of the fact that it can suppress the generation of HFC-134 and, more preferably, can efficiently remove HFC-134 from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. In the present disclosure, a specific beta zeolite can be used among commercially available products.

[0071] (iv) Y-type zeolite Y-type zeolite has pores with an entrance diameter of approximately 0.74 nm, which is the largest among commercially available zeolites. It is a zeolite with large pores.

[0072] In the present disclosure, Y-type zeolite is used because it can efficiently dehydrate compositions containing fluorinated hydrocarbon compounds such as HFC-134a, and the release of water from the zeolite is effectively suppressed even over the course of the dehydration treatment, and more preferably because it can efficiently remove HFC-134 from compositions containing fluorinated hydrocarbon compounds such as HFC-134a. In the present disclosure, a specific Y-type zeolite can be used from among commercially available products.

[0073] Zeolite pore size In the present disclosure, a zeolite having an average pore diameter of preferably 3 Å to 15 Å is used because it allows for efficient dehydration of a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and effectively suppresses water release from the zeolite even over the course of the dehydration treatment, and more preferably allows for efficient removal of HFC-134 from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. In the present disclosure, the average pore diameter of the zeolite used is more preferably 4 Å to 12 Å, and particularly preferably 5 Å to 10 Å.

[0074] In the present disclosure, the zeolite is preferably porous.

[0075] In the present disclosure, the average pore diameter of the zeolite used is 3 Å to 15 Å, so that the zeolite contained in the composition When the fluorine-containing hydrocarbon compounds to be used are preferably compounds having 2 carbon atoms (C2 compounds) to 8 carbon atoms (C8 compounds), and more preferably C2 compounds to C4 compounds, there is an advantage that a dehydration treatment can be efficiently carried out from a composition containing a fluorine-containing hydrocarbon compound such as HFC-134a, and more preferably an advantage that HFC-134 can be efficiently removed from a composition containing a fluorine-containing hydrocarbon compound such as HFC-134a.

[0076] Zeolite cationic species In the present disclosure, the cation of zeolite is preferably used in order to efficiently dehydrate a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and to effectively suppress the release of water from the zeolite even after the elapse of the dehydration treatment time, and more preferably to efficiently remove HFC-134 from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. The species (cationic species) is preferably H + , Li + , Na + , K. + , Ca 2+ , Mg 2+ , Ba 2+ etc., more preferably H + , Na + Cationic zeolites such as the above can be preferably used.

[0077] In the present disclosure, the cations in the zeolite can efficiently perform the dehydration treatment by electrostatically interacting with water.

[0078] Specific surface area of ​​zeolite In the present disclosure, the specific surface area of ​​the zeolite measured by the BET method (hereinafter also referred to as BET specific surface area) is preferably 50 m or less, from the viewpoint that a dehydration treatment can be efficiently performed from a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and that release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time, and more preferably, from the viewpoint that HFC-134 can be efficiently removed from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. 2 / g~3,000m 2 / g, more preferably 100m 2 / g~1,000m 2 / g, more preferably 200m 2 / g~800m 2 / g, and particularly preferably 250m 2 / g~700m 2 / g.

[0079] In the present disclosure, when the BET specific surface area of ​​the zeolite catalyst is within this range, the zeolite The density of the particles is not too small, which has the advantage that dehydration treatment can be carried out efficiently, and more preferably, the advantage that HFC-134 can be efficiently removed from a composition containing a fluorinated hydrocarbon compound such as HFC-134a.

[0080] Zeolite properties The zeolites used in the present disclosure are preferably porous.

[0081] In the present disclosure, the zeolite used may be in the form of powder, granules, or pellets, or may be used as a molded body. From an industrial perspective, it is preferable to use the zeolite as a molded body. There is no particular limitation on the shape of the molded body, but for example, it may be about 0.5 mm to 5 mm in diameter and 1 mm in length. It is preferable to use a cylindrical shape with a diameter of about 15 mm or a spherical shape with a diameter of about 0.5 mm to 10 mm.

[0082] In the present disclosure, there are no particular limitations on the method for producing a zeolite molded body, and for example, a conventionally known method using kaolin clay as a binder can be employed.

[0083] The zeolites used in this disclosure are commercially available.

[0084] Preferred Zeolites In the present disclosure, as explained above, the zeolite is preferred because it can efficiently dehydrate a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and the release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time, and more preferably because it can efficiently remove HFC-134 from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. or a silica-alumina ratio (SiO2 / Al2O3 ratio) (molar ratio) of 5 or more, and is selected from chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. At least one zeolite selected from the group consisting of:

[0085] (1-3) A step of contacting a composition containing a fluorine-containing hydrocarbon compound with a zeolite The method for dehydrating a composition containing a fluorine-based hydrocarbon compound according to the present disclosure includes a step of contacting the composition containing a fluorine-based hydrocarbon compound with a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more, and / or a step of contacting the composition with at least one zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. The dehydration method preferably further comprises the step of contacting the composition containing the fluorinated hydrocarbon compound with the zeolite to remove HFC-134.

[0086] In the present disclosure, contacting the composition with the zeolite means passing the composition through a column or the like packed with the zeolite, or packing the composition into a container packed with the zeolite.

[0087] In the present disclosure, the zeolite is used as a moisture remover (dehydrating agent), and the moisture contained in a composition containing a fluorinated hydrocarbon compound is removed by contacting (passing) the zeolite with the composition. Remove.

[0088] In the present disclosure, to effectively remove water (dehydration), it is further preferable to use HFC-134 In order to effectively remove the above, the composition containing a fluorine-based hydrocarbon compound and the zeolite are mixed in a mass ratio (composition containing a fluorine-based hydrocarbon compound:zeolite) of preferably 100:1 to 100:1. The contact ratio is preferably about 1:10, more preferably about 50:1 to 1:5, and even more preferably about 10:1 to 1:3. In the present disclosure, the amount of zeolite used is, for example, 10 g of zeolite packed (stainless steel). A composition containing a fluorine-based hydrocarbon compound is poured into a cylinder (such as a glass cylinder) in the range of about 10 g to 100 g. can be contacted with

[0089] In the present disclosure, the zeolite may be activated before use. The activation conditions are preferably in a vacuum (10 -1 mmHg~10 -3 Examples of drying treatments include heating overnight at a temperature within a range of 150°C to 300°C, which is a temperature range that allows the zeolite crystal structure to be maintained, under a flow of inert gas such as nitrogen or the like at a pressure of 2000 kJ / cmHg.

[0090] In the present disclosure, zeolites that have not been subjected to the activation treatment can also be suitably used.

[0091] In the present disclosure, the form of use of the zeolite is not particularly limited. A composition containing a fluorinated hydrocarbon compound may be circulated through an apparatus filled with the zeolite, or a composition containing a fluorinated hydrocarbon compound may be filled into a container filled with the zeolite and then removed after a predetermined time has elapsed.

[0092] In the present disclosure, there are no particular limitations on the temperature at which the composition containing a fluorine-based hydrocarbon compound is contacted with the zeolite. The temperature may be determined taking into consideration the boiling point of the fluorine-based hydrocarbon compound, such as HFC-134a, contained in the composition containing a fluorine-based hydrocarbon compound. In general, contacting at a low temperature is preferred because it suppresses side reactions, such as isomerization of the fluorine-based hydrocarbon compound, during contact. The preferred temperature is in the range of approximately -50°C to 100°C.

[0093] In the present disclosure, there is no particular limitation on the time for which the composition containing a fluorinated hydrocarbon compound is brought into contact with the zeolite.

[0094] Preferred Contacting Step In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the contacting step includes a step of contacting the composition containing a fluorinated hydrocarbon compound such as HFC-134a with (i) a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more, and (ii) a chabazite-type zeolite, From the group consisting of mordenite-type zeolite, beta-type zeolite, and Y-type zeolite The step may be any one of the steps of contacting the zeolite with at least one selected from the group consisting of (iii) contacting the zeolite with a silica-alumina (SiO2 / Al2O3) ratio of 5 or more. and contacting the resulting mixture with at least one zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. A method in which the step of contacting the substrate with the substrate is combined with the step of contacting the substrate with the substrate may also be used.

[0095] In the method for dehydrating a composition containing a fluorine-based hydrocarbon compound according to the present disclosure, the contacting step is carried out by contacting the composition containing a fluorine-based hydrocarbon compound such as HFC-134a with (iv) at least one zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more and selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. The step may be a step of contacting the polymer with a polymer.

[0096] (1-4) Gas-phase contact process In the present disclosure, a method for dehydrating a composition containing a fluorine-based hydrocarbon compound includes the steps of contacting the composition containing a fluorine-based hydrocarbon compound with a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more, as described above, and contacting the composition with at least one zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. and / or a step of contacting a silica-alumina (SiO2 / Al2O3) having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more with a chabadite. Zeolite type, mordenite type, beta type, and Y type zeolite In the step of contacting the catalyst with at least one zeolite selected from the group consisting of zeolites, it is preferred that the step be carried out in the gas phase.

[0097] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the contacting step is preferably carried out in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor. When carried out in a gas phase continuous flow system, the apparatus, operation, etc. can be simplified and it is economically advantageous.

[0098] Temperature of the gas-phase contact process In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, there are no particular limitations on the temperature at which the composition containing the fluorinated hydrocarbon compound is brought into contact with a specific zeolite in a gas phase.

[0099] In the contacting step according to the present disclosure, the lower limit of the temperature for contacting in the gas phase is preferably −30° C., more preferably −20° C., from the viewpoints that a composition containing a fluorinated hydrocarbon compound such as HFC-134a can be efficiently dehydrated and that release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time, and more preferably that HFC-134 can be efficiently removed from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. .

[0100] In the contacting step of the present disclosure, the upper limit of the temperature for contacting in the gas phase is about 100°C. do.

[0101] In the contacting step of the present disclosure, the temperature for contacting in the gas phase is preferably low because the adsorption force is strong. In the contacting step of the present disclosure, the temperature for contacting in the gas phase is most preferably room temperature, taking into consideration the operation and handling of the equipment.

[0102] Gas phase contact time In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, there is no particular limitation on the time for which the composition containing the fluorinated hydrocarbon compound is brought into contact with a specific zeolite in the gas phase.

[0103] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, when the method is carried out in a gas phase, the reaction temperature and reaction time (contact time) for the contacting can be appropriately adjusted to efficiently dehydrate a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and the dehydration treatment has the advantage that the release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time, and more preferably, the dehydration treatment can be efficiently carried out from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. The advantage is that it can be removed.

[0104] Pressure during gas-phase contact process In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, there is no particular limitation on the pressure at which the composition containing the fluorinated hydrocarbon compound is brought into contact with a specific zeolite in a gas phase.

[0105] In the chlorination reaction step of the present disclosure, the pressure for contact is preferably set at a pressure that can efficiently dehydrate a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and that can effectively suppress the release of water from the zeolite even after the elapse of the dehydration treatment time, and more preferably, can efficiently dehydrate HFC-134 from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. From the viewpoint of being able to remove the solvent, the pressure is preferably from −0.05 MPa to 2 MPa, more preferably from −0.01 MPa to 1 MPa, and even more preferably from normal pressure to 0.5 MPa.

[0106] In this disclosure, pressure refers to gauge pressure unless otherwise specified.

[0107] Gas-phase contact vessel In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the reactor used to bring the composition containing the fluorinated hydrocarbon compound into contact with a specific zeolite in a gas phase is not particularly limited in shape or structure, as long as it can withstand the above-mentioned temperatures and pressures. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multi-tubular reactor. Examples of the reactor material include glass, stainless steel, iron, nickel, and an iron-nickel alloy.

[0108] Example of a gas-phase contact process The method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure can be carried out in a gas phase by either a flow system or a batch system, in which the composition containing the fluorinated hydrocarbon compound is continuously contacted with a specific zeolite in the reactor and the dehydrated fluorinated hydrocarbon compound is continuously withdrawn from the reactor. The flow system is preferably used so that the dehydrated fluorinated hydrocarbon compound does not remain in the reactor.

[0109] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the step of contacting the composition containing a fluorinated hydrocarbon compound with a specific zeolite is preferably carried out in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor. When carried out in a gas phase continuous flow system, the apparatus, operation, etc. can be simplified and it is economically advantageous.

[0110] In the method for dehydrating a composition containing a fluorine-based hydrocarbon compound according to the present disclosure, the dehydration treatment in the gas phase may be carried out in the presence of an inert gas in order to prevent deterioration of the zeolite. The inert gas is preferably at least one selected from the group consisting of nitrogen, helium, argon, and carbon dioxide. Among these inert gases, a low-cost inert gas is preferred. Nitrogen is more preferred from the viewpoint of suppressing the above-mentioned problem. The concentration of the inert gas is preferably 0 to 50 mol % of the gas components introduced into the reactor.

[0111] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the dehydration treatment is carried out in a gas phase, preferably in an atmosphere free of an inert gas.

[0112] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the composition containing the fluorinated hydrocarbon compound is brought into contact with a specific zeolite in a gas phase, and then, if necessary, purified according to a conventional method to obtain a dehydrated fluorinated hydrocarbon compound.

[0113] In the method for dehydrating a composition containing a fluorine-based hydrocarbon compound disclosed herein, the composition containing the fluorine-based hydrocarbon compound is brought into contact with a specific zeolite in the gas phase, thereby enabling efficient dehydration treatment from a composition containing a fluorine-based hydrocarbon compound such as HFC-134a, and has the advantage that release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time. Also, more preferably, it is possible to efficiently remove HFC-134 from a composition containing a fluorine-based hydrocarbon compound such as HFC-134a. The advantage is that it can be removed.

[0114] (1-5) Liquid phase contact process In the present disclosure, the method for dehydrating a composition containing a fluorine-based hydrocarbon compound preferably comprises the steps of contacting the composition containing a fluorine-based hydrocarbon compound with a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more, contacting the composition with a chabazite-type zeolite, and / or contacting the composition with a chabazite-type zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more, as described above, in a liquid phase.

[0115] Solvent for liquid-phase contact process In the method for dehydrating a composition containing a fluorinated hydrocarbon compound disclosed herein, when the method is carried out in a liquid phase, If the hydrocarbon compound is in a liquid state, no solvent is particularly required.

[0116] Temperature of the liquid phase contact process In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, there are no particular limitations on the temperature at which the composition containing the fluorinated hydrocarbon compound is brought into contact with a specific zeolite in a liquid phase.

[0117] In the contacting step according to the present disclosure, the lower limit of the temperature for contacting in the liquid phase is preferably −30° C., more preferably −20° C., from the viewpoints that a composition containing a fluorinated hydrocarbon compound such as HFC-134a can be efficiently dehydrated and that release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time, and more preferably that HFC-134 can be efficiently removed from a composition containing a fluorinated hydrocarbon compound such as HFC-134a. .

[0118] In the contacting step of the present disclosure, the upper limit of the temperature for contacting in the liquid phase is about 100°C. do.

[0119] In the contacting step of the present disclosure, the temperature for contacting in the liquid phase is preferably low because the adsorption force is strong. In the contacting step of the present disclosure, the temperature for contacting in the liquid phase is most preferably room temperature, taking into consideration the operation and handling of the equipment.

[0120] Pressure during contact process in liquid phase In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, there is no limitation on the reactor as long as the composition containing the fluorinated hydrocarbon compound can be brought into contact with a specific zeolite in a liquid phase. The liquid phase conditions may be such that the composition containing the fluorinated hydrocarbon compound is satisfactorily liquefied, and the reaction may be carried out under the saturated vapor pressure of the fluorinated hydrocarbon compound.

[0121] Closed and / or pressurized liquid-phase reaction systems In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the pressure in a reactor is not particularly limited as long as the composition containing the fluorinated hydrocarbon compound can be brought into contact with a specific zeolite in a liquid phase.

[0122] In the method for dehydrating a composition containing a fluorine-containing hydrocarbon compound according to the present disclosure, the step of contacting the composition containing the fluorine-containing hydrocarbon compound with a specific zeolite in a liquid phase is preferred because it allows efficient dehydration treatment from a composition containing a fluorine-containing hydrocarbon compound such as HFC-134a, and the release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time, and more preferably, it allows efficient dehydration treatment from a composition containing a fluorine-containing hydrocarbon compound such as HFC-134a, and the release of water from the zeolite is well suppressed even after the elapse of the dehydration treatment time. The reaction can be preferably carried out in a closed reaction system and / or a pressurized reaction system, since the reaction can be carried out in a closed reaction system and / or a pressurized reaction system.

[0123] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the reactor for bringing the composition containing the fluorinated hydrocarbon compound into contact with a specific zeolite in a liquid phase is not particularly limited in shape and structure, as long as it can withstand the reaction.

[0124] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, it is preferable to carry out the reaction in a sealed liquid phase reaction system using a batch-type pressure-resistant reaction vessel.

[0125] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, in a pressurized reaction system in a liquid phase, the reaction pressure is preferably equal to or higher than the saturated vapor pressure of the target fluorinated hydrocarbon compound, in order to ensure liquefaction.

[0126] In this disclosure, reaction pressures are gauge pressures unless otherwise specified.

[0127] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound disclosed herein, the reactor used in the sealed and / or pressurized liquid-phase reaction system is not limited. However, it is preferable to charge the composition containing the fluorinated hydrocarbon compound into a pressure vessel such as an autoclave, heat the mixture to an appropriate reaction temperature using a heater, and carry out the reaction for a certain period of time while stirring. Examples of reactor materials include glass, stainless steel, iron, nickel, and iron-nickel alloys. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen, helium, or carbon dioxide. For example, the reaction is preferably carried out using a batch-type pressure-resistant reaction vessel (such as an autoclave) to seal the reaction system. Examples of reactor materials include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0128] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the reaction pressure of the pressurized reaction system in the liquid phase is the pressure inside a reaction vessel used in the pressurized reaction system. In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the reaction pressure under which the composition containing the fluorinated hydrocarbon compound is brought into contact with a specific zeolite is preferably a pressure under which liquefaction can be achieved, more preferably 0.5 MPa or more, even more preferably 0.7 MPa or more, and particularly preferably 1.0 MPa or more, in order to efficiently dehydrate the composition containing a fluorinated hydrocarbon compound such as HFC-134a and to effectively suppress release of water from the zeolite even after the elapse of the dehydration treatment time.

[0129] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the upper limit of the reaction pressure when the composition containing the fluorinated hydrocarbon compound is brought into contact with the specific zeolite in a liquid phase is generally about 1.0 MPa, for the same reasons as above. The pressure in the reaction system can be increased by feeding an inert gas such as nitrogen, helium, or carbon dioxide into the reaction system.

[0130] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the step of contacting the composition containing a fluorinated hydrocarbon compound with a specific zeolite in a liquid phase may also be carried out in a continuous, pressurized reaction mode while withdrawing a liquid or while gasifying and withdrawing a product, for example, by connecting a back pressure valve to a continuous phase tank reactor (CSTR).

[0131] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the composition containing the fluorinated hydrocarbon compound is brought into contact with a specific zeolite in a liquid phase, and then, if necessary, purified according to a conventional method to obtain a dehydrated fluorinated hydrocarbon compound.

[0132] In the method for dehydrating a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the composition containing the fluorinated hydrocarbon compound is brought into contact with a specific zeolite in a liquid phase, in a closed reaction system and / or a pressurized reaction system, thereby enabling efficient dehydration treatment from a composition containing a fluorinated hydrocarbon compound such as HFC-134a, and has the advantage that release of water from the zeolite is well suppressed even over the course of the dehydration treatment, and more preferably, the advantage that HFC-134 can be efficiently removed from a composition containing a fluorinated hydrocarbon compound such as HFC-134a.

[0133] (1-6) The moisture content and / or HFC-134 content must be less than 3 ppmwt. According to the method for dehydrating a composition containing a fluorinated hydrocarbon compound disclosed herein, when dehydrating a composition containing a fluorinated hydrocarbon compound such as HFC-134a, the silica alumina (SiO2 / Al2O3) Zeolites with a ratio of 5 or more, chabazite-type zeolites, mordenite-type zeolites, and benzyl zeolites At least one zeolite selected from the group consisting of zeolite type A and zeolite type Y. By using zeolite, the release of moisture adsorbed in the zeolite is suppressed even over time.

[0134] According to the method for dehydrating a composition containing a fluorinated hydrocarbon compound of the present disclosure, the water content in the composition containing a fluorinated hydrocarbon compound such as HFC-134a after dehydration, i.e., the composition after contacting with the zeolite, is reduced to less than about 10 ppmwt (mass / mass). In the present disclosure, the minimum water content in the composition after dehydration is about 0.1 ppmwt.

[0135] According to the method for dehydrating a composition containing a fluorinated hydrocarbon compound of the present disclosure, the content of HFC-134 in the composition containing a fluorinated hydrocarbon compound such as HFC-134a in the dehydrated composition, i.e., the composition after contact with the zeolite, can be reduced to less than about 10 ppmwt (mass / mass), and preferably less than about 3 ppmwt. In the present disclosure, the minimum content of HFC-134 in the dehydrated composition is about 0.1 ppmwt.

[0136] According to the method for dehydrating a composition containing a fluorinated hydrocarbon compound of the present disclosure, it is more preferable that the water content in a composition containing a fluorinated hydrocarbon compound such as HFC-134a be less than about 3 ppmwt, and the HFC-134 content be less than about 3 ppmwt.

[0137] According to the present disclosure, by effectively dehydrating (removing) the amount of water in a composition containing a fluorinated hydrocarbon compound such as HFC-134a, the fluorinated hydrocarbon compound such as HFC-134a from which the water has been dehydrated (removed) can be used as a fluorinated hydrocarbon compound such as HFC-134a, more preferably as a fluorinated hydrocarbon compound such as HFC-134a from which HFC-134 has been removed. The elemental compounds can be suitably used as etching gases for semiconductor manufacturing, and can also suppress corrosion and early deterioration of equipment.

[0138] (2) Method for producing a composition containing a fluorinated hydrocarbon compound In the method for producing a composition containing a fluorine-containing hydrocarbon compound according to the present disclosure, the fluorine-containing hydrocarbon compound is at least one selected from the group consisting of HFC-134a, HFC-125, HFC-32, and HFO-1234yf. The method includes a step of contacting a composition containing the fluorine-containing hydrocarbon compound with a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more.

[0139] In the method for producing a composition containing a fluorine-containing hydrocarbon compound according to the present disclosure, the fluorine-containing hydrocarbon compound is at least one selected from the group consisting of HFC-134a, HFC-125, HFC-32, and HFO-1234yf. The composition containing the fluorine-containing hydrocarbon compound is mixed with a chabazite-type zeolite, a mordenite-type zeolite, a beta-type zeolite, and a Y-type zeolite. with at least one zeolite selected from the group consisting of:

[0140] The method for producing a composition containing a fluorinated hydrocarbon compound according to the present disclosure preferably further comprises contacting the composition containing the fluorinated hydrocarbon compound with the zeolite to remove HFC-134. The method includes the step of:

[0141] The step of contacting the composition containing the fluorine-containing hydrocarbon compound with various zeolites can be the same as the step in the dehydration method described above.

[0142] In the method for producing a composition containing a fluorine-containing hydrocarbon compound according to the present disclosure, the water content of the composition after contact with the zeolite is less than about 10 ppmwt, preferably less than about 3 ppmwt. In the present disclosure, the minimum water content in the composition is about 0.1 ppmwt.

[0143] In the method for producing a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the content of HFC-134 in the composition after contact with the zeolite is less than about 10 ppmwt, preferably less than about 3 ppmwt. In the present disclosure, the minimum content of HFC-134 in the composition is about 0.1 ppmwt.

[0144] In the method for producing a composition containing a fluorine-based hydrocarbon compound according to the present disclosure, the composition after contacting with the zeolite preferably has a water content of less than about 3 ppmwt and a content of HFC-134 of less than about 1 ppmwt. The amount is less than about 3 ppmwt.

[0145] The manufacturing method of the present disclosure is to add 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), or 1,1,1,2-pentafluoroethane (HFC-125) to a zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more. and removing impurities contained in the fluorine-containing hydrocarbon compound.

[0146] The manufacturing method of the present disclosure includes producing at least one zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. The fluorine-containing hydrocarbon compound is contacted with at least one selected from the group consisting of 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3-tetrafluoropropene (HFO-1234yf). and removing impurities contained in the fluorine-containing hydrocarbon compound. The impurities are preferably at least one selected from the group consisting of water and HFC-134. It is a type of ingredient.

[0147] The step of contacting the composition containing the fluorine-containing hydrocarbon compound with various zeolites can be the same as the step in the dehydration method described above.

[0148] In the manufacturing method of the present disclosure, the impurities to be removed are, for example, the water described above. The water concentration contained in the fluorine-based hydrocarbon compound after the impurity removal is 10 ppmwt or less. In the present disclosure, the minimum water content is about 0.1 ppmwt.

[0149] In the manufacturing method of the present disclosure, the impurities to be removed are, for example, HFC-134 as described above. The concentration of HFC-134 contained in the fluorinated hydrocarbon compound after the impurity removal is less than about 10 ppmwt, and preferably less than about 3 ppmwt. In the present disclosure, the minimum value of the HFC-134 content is about 0.1 ppmwt.

[0150] The water concentration and HFC-134 concentration contained in the fluorinated hydrocarbon compound after the impurity removal are More preferably, the water content is less than about 3 ppmwt and the HFC-134 content is less than about 3 ppmwt. be.

[0151] In the present disclosure, the step preferably involves adsorbing water onto the zeolite from the composition containing the fluorinated hydrocarbon compound, thereby dehydrating the composition, and removing water from the composition before contacting it with the zeolite. Also, more preferably, the step involves removing HFC-134 from the composition containing the fluorinated hydrocarbon compound.

[0152] In the method for producing a composition containing a fluorine-containing hydrocarbon compound according to the present disclosure, the contacting step is carried out by contacting the composition containing a fluorine-containing hydrocarbon compound such as HFC-134a with a silica-alumina (SiO2 / Al2O3) ratio a step of contacting the zeolite with a molecular weight of 5 or more and a step of contacting the zeolite with a chabazite-type zeolite or a mordenite-type zeolite at least one selected from the group consisting of zeolite, beta zeolite, and Y zeolite; The step of contacting the zeolite with a silica-alumina (SiO2 / Al2O3) ratio of 5 or more and the step of contacting the zeolite with a chabazite-type zeolite may be either one of the steps. Zeolite, mordenite, beta, and Y zeolite The process may be a combined process with a process of contacting the catalyst with at least one zeolite selected from the group consisting of:

[0153] In the method for producing a composition containing a fluorinated hydrocarbon compound according to the present disclosure, the contacting step is carried out by contacting the composition containing a fluorinated hydrocarbon compound such as HFC-134a with a silica-alumina (SiO2 / Al2O3) The ratio is 5 or more, and chabazite-type zeolite, mordenite-type zeolite, and beta-type zeolite are At least one zeolite selected from the group consisting of zeolite and Y-type zeolite The step of contacting the

[0154] In the present disclosure, the amount of water in the composition after contact with the zeolite, particularly in the composition containing a fluorinated hydrocarbon compound such as HFC-134a, can be preferably less than 3 ppmwt.

[0155] In the present disclosure, the content of HFC-134 in the composition after contact with the zeolite, particularly in the composition containing a fluorinated hydrocarbon compound such as HFC-134a, is preferably less than 3 ppmwt. It is possible to do this.

[0156] In the method for producing a composition containing a fluorine-based hydrocarbon compound according to the present disclosure, the composition containing a fluorine-based hydrocarbon compound to be dehydrated, the zeolite to be used, the step of contacting the composition containing a fluorine-based hydrocarbon compound with the zeolite, the contact step in the gas phase, the contact step in the liquid phase, reducing the water content to less than 3 ppmwt, and reducing the HFC-134 content to less than 3 ppmwt, etc., are the same as those described above in the present disclosure. This is as explained in the above method for dehydrating a composition containing a fluorinated hydrocarbon compound.

[0157] (3) Composition containing a fluorinated hydrocarbon compound In the composition containing a fluorine-containing hydrocarbon compound of the present disclosure, the fluorine-containing hydrocarbon compound is at least one selected from the group consisting of HFC-134a, HFC-125, HFC-32, and HFO-1234yf. and has a water content of less than 3 ppmwt.

[0158] In the composition containing a fluorine-containing hydrocarbon compound of the present disclosure, the fluorine-containing hydrocarbon compound is at least one selected from the group consisting of HFC-134a, HFC-125, HFC-32, and HFO-1234yf. and contains less than 3 ppmwt of HFC-134.

[0159] The composition containing the fluorinated hydrocarbon compound of the present disclosure more preferably has a water content of less than 3 ppmwt and an HFC-134 content of less than 3 ppmwt.

[0160] Moisture measurement The water content of the composition containing a fluorinated hydrocarbon compound of the present disclosure is the water content measured using a Karl Fischer moisture meter, and is the water content based on the Karl Fischer method. Specifically, it refers to the value measured by titration after adding 1 g of a composition (liquefied gas) containing a fluorinated hydrocarbon compound to the Karl Fischer moisture meter and collecting the water in a solvent.

[0161] The water content (ppm) is the amount of water (by mass) contained in a composition containing a fluorinated hydrocarbon compound. , the mass fraction divided by the mass of the composition containing the fluorinated hydrocarbon compound, i.e., ppmwt (mass / mass) (quantity).

[0162] Measurement of HFC-134 content The HFC-134 content of the composition containing the fluorinated hydrocarbon compound of the present disclosure was determined by mass spectrometry and structural analysis. It is possible to measure this based on structural analysis.

[0163] The content of HFC-134 in the composition containing the fluorinated hydrocarbon compound of the present disclosure is, for example, Using a gas chromatograph (for example, Shimadzu Corporation, product name "GC-2014"), Mass analysis is performed by GC / MS, and then structural analysis is performed by NMR spectroscopy (for example, JEOL's product name "400YH"). , can be measured.

[0164] In this disclosure, the content (ppm) of HFC-134 when using these devices is calculated by dividing the content (volume) of HFC-134 contained in a composition containing a fluorinated hydrocarbon compound by the volume of the fluorinated hydrocarbon compound. The volume fraction is the volume fraction divided by the volume of the composition containing the elemental compound, i.e., ppmvol (vol / vol). The content (ppm) of HFC-134 can be expressed as, for example, less than 3 ppmvol.

[0165] The composition containing the fluorine-based hydrocarbon compound of the present disclosure is used as an etching gas for forming cutting-edge microstructures in semiconductors, liquid crystals, etc., similar to HFC-134a, HFC-125, HFC-32, HFO-1234yf, etc. In addition, the composition containing the fluorinated hydrocarbon compound of the present disclosure can be effectively used for various purposes such as an etching gas, a deposit gas, a building block for organic synthesis, a cleaning gas, and the like.

[0166] Compositions containing the fluorinated hydrocarbon compounds of the present disclosure are preferably used as etching gases, refrigerants, heat transfer media, deposition gases, building blocks for organic synthesis, or cleaning gases.

[0167] The deposition gas is a gas that deposits an etch-resistant polymer layer.

[0168] The building block for organic synthesis refers to a substance that can be a precursor to a compound having a highly reactive skeleton. For example, by reacting a composition containing the fluorine-containing hydrocarbon compound of the present disclosure with a fluorine-containing organosilicon compound such as CF3Si(CH3)3, a fluoroalkyl group such as a CF3 group can be introduced to convert the compound into a substance that can be used as a cleaning agent or a fluorine-containing pharmaceutical intermediate.

[0169] Although the embodiments of the present disclosure have been described above, various changes in form and details are possible without departing from the spirit and scope of the claims. [Example]

[0170] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples in any way.

[0171] Measurement of water content in compositions containing fluorinated hydrocarbon compounds The moisture content was measured using the following measuring device, conditions and method.

[0172] Measuring device: Karl Fischer moisture meter Measurement conditions: Coulometric titration method

[0173] The water content of the composition containing a fluorinated hydrocarbon compound was measured using a Karl Fischer moisture meter, and was based on the coulometric titration method of the Karl Fischer method. Specifically, 1 g of the composition containing a fluorinated hydrocarbon compound was placed in the Karl Fischer moisture meter, the water was collected in a solvent, and the value measured by titration was used.

[0174] The water content (ppm) is the amount of water (by mass) contained in a composition containing a fluorinated hydrocarbon compound. , the mass fraction divided by the mass of the composition containing the fluorinated hydrocarbon compound, i.e., ppmwt (mass / mass) amount).

[0175] (1) Method for dehydrating a composition containing a fluorinated hydrocarbon compound of the embodiment (liquid phase) Fluorinated hydrocarbon compounds: HFC-134a A composition containing HFC-134a was contacted with a chabazite-type zeolite (Example 1), a mordenite-type zeolite (Example 2), a beta-type zeolite (Example 3), or a Y-type zeolite (Example 4), each having a silica-alumina (SiO / AlO) ratio of 5 or more.

[0176] 1 g of each zeolite (dehydrating agent) shown in Table 1 was packed into a 75 mL stainless steel cylinder. The cylinder was filled with a composition containing a specified amount (10 g) of HFC-134a. ,From the start of dehydration (0 hr), 24 hours later (24 hr), 48 hours later (48 hr), 72 hours later (72 hr), 96 After 96 hours, the water content of the liquid phase was measured by Karl Fischer.

[0177] [Table 1]

[0178] The water content of the composition after contact with each of the zeolites in the Examples was less than 3 ppmwt. When a chabazite-type zeolite with a silica-alumina (SiO2 / Al2O3) ratio of 5 or more was used as a dehydrating agent, water was not desorbed from the zeolite over time, and no increase in the water content in the composition containing HFC-134a was observed.

[0179] (2) Comparative Example: Dehydration Method of Composition Containing Fluorinated Hydrocarbon Compound (Liquid Phase) A composition containing HFC-134a was contacted with a type A zeolite having a silica-alumina (SiO2 / Al2O3) ratio of less than 5 and which was not of the chabazite type.

[0180] 1 g of each zeolite (dehydrating agent) shown in Table 2 was packed into a 75 mL stainless steel cylinder. The cylinder was filled with a composition containing a specified amount (10 g) of HFC-134a. ,From the start of dehydration (0 hr), 24 hours later (24 hr), 48 hours later (48 hr), 72 hours later (72 hr), 96 After 96 hours, the water content of the liquid phase was measured by Karl Fischer.

[0181] [Table 2]

[0182] In the composition after contact with each zeolite of the comparative examples, the water content exceeded 3 ppmwt. When a zeolite with a silica-alumina (SiO2 / Al2O3) ratio of about 2 was used as a dehydrating agent, the water content increased over time. As a result, the adsorbed water was desorbed from the zeolite, and an increase in the water content in the composition containing HFC-134a was observed.

[0183] (3) Method for dehydrating a composition containing a fluorinated hydrocarbon compound in a gas phase Fluorinated hydrocarbon compounds: HFC-134a This HFC-134a is a sample containing 5 ppmwt (mass / mass) of water.

[0184] The zeolite (molecular sieves (MS)) used was heated in a vacuum (10 -1 mmHg~10 -3 Activation is achieved by removing water from the zeolite by heating at 180°C under pressure (mmHg). Processed (pre-processed).

[0185] A composition (gas) containing HFC-134a was mixed with a chabazite-type zeolite (Example 8) having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more, and a silica-alumina (SiO2 / Al2O3) ratio of less than 5. The HFC-134a was contacted with a non-chabazite-type A-type zeolite (Comparative Examples 9 and 10) containing HFC-134a. The gas phase dehydration method was performed by passing a gas containing HFC-134a through a zeolite layer under conditions of W / F = 0.2 to 0.6 g / (cc / sec) and a flow rate of HFC-134a of 1.7 cm / sec.

[0186] [Table 3]

[0187] The zeolite of Example 8 efficiently and in a short time produced the following from a composition (gas) containing HFC-134a: Furthermore, by activating (pre-treating) the zeolite before use, water can be removed more efficiently and in a shorter time from the composition (gas) containing HFC-134a.

[0188] On the other hand, the zeolites of Comparative Examples 9 and 10 efficiently absorbed the HFC-134a-containing composition (gas). It was not possible to remove the water.

[0189] (4) Method for removing HFC-134 from compositions containing fluorinated hydrocarbon compounds in the gas phase Fluorinated hydrocarbon compounds: HFC-134a This HFC-134a is a sample containing 5 ppmwt (mass / mass) water and 500 ppmvol (volume / volume) HFC-134.

[0190] The zeolite (molecular sieves (MS)) used was heated in a vacuum (10 -1 mmHg~10 -3 Activation is achieved by removing water from the zeolite by heating at 180°C under pressure (mmHg). Processed (pre-processed).

[0191] A composition (gas) containing HFC-134a was contacted with a chabazite-type zeolite having a silica-alumina (SiO2 / Al2O3) ratio of 5 or more (Example 11) and with a non-chabazite-type A-type zeolite having a silica-alumina (SiO2 / Al2O3) ratio of less than 5 (Comparative Examples 12 and 13). The method for removing HFC-134 in the phase is to pass a gas containing HFC-134a through a layer of zeolite with a W / F of 100g. / (cc / sec) until HFC-134 concentration was detected at the outlet.

[0192] [Table 4]

[0193] The zeolite of Example 11 was heated in a gas atmosphere containing HFC-134a under the condition of W / F=100 g / (cc / sec). Even after flowing HFC-134 for 12 hours, no breakthrough occurred and no HFC-134 was detected. The method can remove HFC-134 efficiently and in a short time. Furthermore, by subjecting the zeolite to an activation treatment (pretreatment) before use, it is possible to remove HFC-134 from a composition (gas) containing HFC-134a more efficiently and in a shorter time. I was able to do it.

[0194] On the other hand, in the case of the zeolites of Comparative Examples 12 and 13, breakthrough occurred in 6 minutes, and HFC-134 was detected, and the amount detected continued to increase. The zeolites of Comparative Examples 12 and 13 were unable to efficiently remove HFC-134 from the composition (gas) containing HFC-134a.

[0195] (5) Description of the chabazite-type (A-similar type) zeolite (MS) used in the examples The chabazite-type (A-similar type) zeolite used in the examples is a zeolite in which the AlO4 in 5A of A-type zeolite, which is a synthetic zeolite, is replaced with SiO4, and its crystal structure is the same as that of chabazite.

[0196] As a result of X-ray diffraction, the crystal system of the chabazite-type (A-similar type) zeolite used in the examples is a mixture of the natural minerals chabazite and erionite, i.e., a chabazite-type synthetic zeolite (chabazite-type zeolite) and an erionite-type synthetic zeolite (erionite). It is a synthetic zeolite mixture with zeolite (a type of zeolite).

[0197] (6) Summary of methods for dehydrating compositions containing fluorinated hydrocarbon compounds As semiconductor integrated circuit devices become faster and more highly integrated, circuit patterns are becoming increasingly finer. Fluorinated hydrocarbon compounds such as HFC-134a are essential gases for etching the finest contact holes.

[0198] The method for dehydrating a composition containing a fluorinated hydrocarbon compound and the method for producing a composition containing a fluorinated hydrocarbon compound according to the present disclosure have the advantage that by using the specific zeolite when dehydrating a composition containing a fluorinated hydrocarbon compound such as HFC-134a, the release of moisture adsorbed by the zeolite is suppressed even over time, and moisture can be effectively removed from the composition containing a fluorinated hydrocarbon compound such as HFC-134a.

[0199] According to the method for dehydrating a composition containing a fluorinated hydrocarbon compound and the method for producing a composition containing a fluorinated hydrocarbon compound of the present disclosure, it is possible to reduce the water content in a composition containing a fluorinated hydrocarbon compound such as HFC-134a to less than 3 ppmwt. A composition containing a fluorinated hydrocarbon compound (such as HFC-134a) with a water content of less than 3 ppmw is advantageous for etching fine contact holes and forming fine circuit patterns in semiconductor integrated circuit devices.

Claims

1. A method for dehydrating a composition containing a fluorinated hydrocarbon compound, comprising: The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- at least one compound selected from the group consisting of tetrafluoropropene (HFO-1234yf), The composition containing the fluorine-containing hydrocarbon compound is mixed with silica alumina (SiO 2 / Al 2 O 3 ) ratio of 5 or more.

2. A method for dehydrating a composition containing a fluorinated hydrocarbon compound, comprising: The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- at least one compound selected from the group consisting of tetrafluoropropene (HFO-1234yf), The composition containing the fluorine-containing hydrocarbon compound is treated with a zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. A method for dehydration comprising contacting with at least one zeolite.

3. 3. The dehydration method according to claim 1, wherein the step reduces the water content of the composition after dehydration to less than 3 ppmwt.

4. 4. The method according to claim 1, further comprising the step of contacting the composition containing the fluorinated hydrocarbon compound with the zeolite to remove 1,1,2,2-tetrafluoroethane (HFC-134). The dehydration method according to claim 1.

5. A method for producing a composition containing a fluorinated hydrocarbon compound, comprising: The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- at least one compound selected from the group consisting of tetrafluoropropene (HFO-1234yf), The composition containing the fluorine-containing hydrocarbon compound is mixed with silica alumina (SiO 2 / Al 2 O 3 ) ratio of 5 or greater.

6. A method for producing a composition containing a fluorinated hydrocarbon compound, comprising: The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- at least one compound selected from the group consisting of tetrafluoropropene (HFO-1234yf), The composition containing the fluorine-containing hydrocarbon compound is treated with a zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite. A method of making the same, comprising the step of contacting with at least one zeolite.

7. 7. The method according to claim 5, wherein the composition after contacting with the zeolite has a water content of less than 3 ppmwt.

8. 8. The method according to claim 5, further comprising the step of contacting the composition containing the fluorinated hydrocarbon compound with the zeolite to remove 1,1,2,2-tetrafluoroethane (HFC-134). The manufacturing method described in

9. Silica alumina (SiO 2 / Al 2 O 3 ) ratio of 5 or more, and a zeolite selected from the group consisting of 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3-tetrafluoropropene (HFO-1234yf). a process for producing a high-purity fluorine-containing hydrocarbon compound, the process comprising the step of contacting a composition containing at least one fluorine-containing hydrocarbon compound with a fluorine-containing hydrocarbon compound to remove impurities contained in the fluorine-containing hydrocarbon compound.

10. At least one type of zeolite selected from the group consisting of chabazite-type zeolite, mordenite-type zeolite, beta-type zeolite, and Y-type zeolite is doped with 1,1,1,2-tetramethylbenzyl ether. Pentafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoroethane 1. A method for producing a high-purity fluorinated hydrocarbon compound, comprising the step of contacting a fluorinated hydrocarbon compound with a composition containing at least one fluorinated hydrocarbon compound selected from the group consisting of 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), thereby removing impurities contained in the fluorinated hydrocarbon compound.

11. The impurities are selected from the group consisting of water and 1,1,2,2-tetrafluoroethane (HFC-134).

11. The dehydration method according to claim 9 or 10, wherein the component is at least one selected from the group consisting of:

12. 12. The method according to claim 9, wherein the water concentration contained in the fluorinated hydrocarbon compound after the impurity removal is less than 3 ppmwt.

13. A composition comprising a fluorinated hydrocarbon compound, The fluorine-based hydrocarbon compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), difluoromethane (HFC-32), and 2,3,3,3- tetrafluoropropene (HFO-1234yf), Compositions containing less than 3 ppmwt of water and / or less than 3 ppmwt of HFC-134 。

14. 14. The composition of claim 13, wherein the composition is used as an etching gas, a refrigerant, a heat transfer medium, a deposition gas, a building block for organic synthesis, or a cleaning gas.

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