WO2022044613A1 - ハロン精製方法 - Google Patents
ハロン精製方法 Download PDFInfo
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- WO2022044613A1 WO2022044613A1 PCT/JP2021/026842 JP2021026842W WO2022044613A1 WO 2022044613 A1 WO2022044613 A1 WO 2022044613A1 JP 2021026842 W JP2021026842 W JP 2021026842W WO 2022044613 A1 WO2022044613 A1 WO 2022044613A1
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- Prior art keywords
- halon
- crude
- purification method
- absorption
- liquid
- Prior art date
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- 229920004449 Halon® Polymers 0.000 title claims abstract description 260
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 title claims abstract description 260
- 238000000746 purification Methods 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 126
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 104
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 103
- 229910001511 metal iodide Inorganic materials 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims description 153
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical group [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 20
- 239000002250 absorbent Substances 0.000 claims description 18
- 230000002745 absorbent Effects 0.000 claims description 18
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical compound FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 6
- 239000001230 potassium iodate Substances 0.000 claims description 6
- 235000006666 potassium iodate Nutrition 0.000 claims description 6
- 229940093930 potassium iodate Drugs 0.000 claims description 6
- GRCDJFHYVYUNHM-UHFFFAOYSA-N bromodifluoromethane Chemical compound FC(F)Br GRCDJFHYVYUNHM-UHFFFAOYSA-N 0.000 claims description 5
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims description 4
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 claims description 4
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 claims description 4
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011697 sodium iodate Substances 0.000 claims description 4
- 235000015281 sodium iodate Nutrition 0.000 claims description 4
- 229940032753 sodium iodate Drugs 0.000 claims description 4
- IHZAEIHJPNTART-UHFFFAOYSA-N tribromofluoromethane Chemical compound FC(Br)(Br)Br IHZAEIHJPNTART-UHFFFAOYSA-N 0.000 claims description 4
- CALRXIQBQWFLRG-UHFFFAOYSA-N 1,1,1-tribromo-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Br)(Br)Br CALRXIQBQWFLRG-UHFFFAOYSA-N 0.000 claims description 3
- MHTDCCPJYMZHSK-UHFFFAOYSA-N 1,1-dibromo-1,2,2-trifluoroethane Chemical compound FC(F)C(F)(Br)Br MHTDCCPJYMZHSK-UHFFFAOYSA-N 0.000 claims description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 3
- -1 bromofluoroethylene, bromodifluoroethylene Chemical group 0.000 claims description 3
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 3
- JLGADZLAECENGR-UHFFFAOYSA-N 1,1-dibromo-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Br)Br JLGADZLAECENGR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 39
- 239000007789 gas Substances 0.000 description 25
- 239000011261 inert gas Substances 0.000 description 24
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000011144 upstream manufacturing Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 description 4
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 229910001640 calcium iodide Inorganic materials 0.000 description 3
- 229940046413 calcium iodide Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LANNRYWUUQMNPF-UHFFFAOYSA-N 1-bromo-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)Br LANNRYWUUQMNPF-UHFFFAOYSA-N 0.000 description 2
- XRZHWZVROHBBAM-UHFFFAOYSA-N 1-bromo-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=CBr XRZHWZVROHBBAM-UHFFFAOYSA-N 0.000 description 2
- JNUYTCRSXFUQHQ-UHFFFAOYSA-N 2-bromo-1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)C(Br)C(F)(F)F JNUYTCRSXFUQHQ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001509 metal bromide Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- YQPBMUIOKYTYDS-UHFFFAOYSA-N 1-bromo-1,2-difluoroethene Chemical group FC=C(F)Br YQPBMUIOKYTYDS-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000872931 Myoporum sandwicense Species 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241001478412 Zizania palustris Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- LHMHCLYDBQOYTO-UHFFFAOYSA-N bromofluoromethane Chemical compound FCBr LHMHCLYDBQOYTO-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 229920013653 perfluoroalkoxyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1487—Removing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
- C07C19/14—Acyclic saturated compounds containing halogen atoms containing fluorine and bromine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/306—Alkali metal compounds of potassium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
- B01D2252/103—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/26—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2022—Bromine
Definitions
- the present invention relates to a method for purifying halon.
- Halon is a compound used as a fire extinguisher, a refrigerant, a synthetic reagent, and the like.
- Halon is a halogenated hydrocarbon in which some or all of hydrogen atoms of saturated or unsaturated hydrocarbons are substituted with halogen atoms, and some or all of the halogen atoms substituting hydrogen atoms are bromine atoms.
- Halon may contain bromine molecules (Br 2 ) as impurities due to its synthesis process or thermal decomposition. However, since bromine molecules are corrosive and toxic, it is preferable to remove them from halon.
- Patent Document 1 proposes a technique of using an aqueous solution of an organic base as an absorbing solution
- Patent Document 2 proposes a technique of using an aqueous solution of a metal sulfite and a metal hydroxide as an absorbing solution.
- An object of the present invention is to provide a halon purification method capable of easily, safely and efficiently removing contaminated bromine molecules to obtain high-purity halon.
- a halon purification method for removing the bromine molecule from a crude halon containing halon and a bromine molecule A contact step of contacting the crude halon with an absorbent solution consisting of an aqueous solution containing a metal iodide to obtain a mixed solution containing the crude halon and the absorbent solution. A separation step of separating the halon from the mixture to obtain the absorption liquid and the halon that have absorbed the bromine molecule.
- a furlong purification method comprising.
- the halon is bromomethane, tribromofluoromethane, bromodifluoromethane, dibromodifluoromethane, bromotrifluoromethane, bromoethane, dibromotrifluoroethane, dibromotetrafluoroethane, tribromotrifluoroethane, bromofluoroethylene, bromodifluoroethylene.
- the halon purification method according to any one of [1] to [4], which is at least one of bromotrifluoroethylene.
- bromine molecules mixed in halon can be easily, safely and efficiently removed to obtain high-purity halon.
- the halon purification method is a halon purification method for removing bromine molecules from crude halon containing halon and bromine molecules, and the crude halon is added to an absorbent solution consisting of an aqueous solution containing a metal iodide. It is provided with a contacting step of contacting to obtain a mixed solution containing crude halon and an absorbing solution, and a separation step of separating halon from the mixed solution to obtain an absorbing solution containing bromine molecules and halon.
- Halon may contain bromine molecules as impurities, but if the crude halon containing halon and bromine molecules is purified by the halon purification method according to the present embodiment, the bromine molecules mixed in the crude halon can be obtained. High-purity purified halon can be obtained by removing it easily, safely and efficiently.
- the halon purification method according to the present embodiment does not use a distillation method, a high-purity purified halon can be easily obtained without the need for a large-scale device such as a distillation column. Further, since the purification is performed by the liquid phase extraction method instead of the purification by the distillation method, high-purity purified halon can be obtained even if the halon has a boiling point close to that of the bromine molecule. Further, since an aqueous solution containing a metal iodide is used as the absorbing liquid without requiring an alkaline solution as the absorbing liquid, the absorption liquid is highly safe and easy to operate. Further, since halon does not come into contact with an alkaline solution and halon is not easily hydrolyzed, bromine molecules can be efficiently removed from crude halon to obtain high-purity purified halon.
- the halon purification method according to this embodiment will be described in more detail below.
- the type of furlong that can be purified by the halon purification method according to the present embodiment is not particularly limited, but the solubility in water is considered in consideration of the ease of separation when separating halon from the mixed solution in the separation step.
- Halong which has a low boiling point, is preferable. That is, halon having 1 or more and 3 or less carbon atoms is preferable, and halon having 1 or 2 carbon atoms is more preferable.
- halon is bromomethane (CH 3 Br), tribromofluoromethane (CBr 3 F), bromodifluoromethane (CHBrF 2 ), dibromodifluoromethane (CBr 2 F 2 ), bromotrifluoromethane (CBrF 3 ).
- the crude halon used in the halon purification method according to the present embodiment may be in the form of a gas or a liquid.
- Halon having a low boiling point such as dibromodifluoromethane, bromotrifluoroethylene, bromohexafluoropropane, bromoheptafluoropropane, and bromotrifluoropropene is suitable for gas-liquid separation, and tribromofluoromethane, tribromotrifluoroethane, etc.
- Halon, which has a high boiling point is suitable for liquid-liquid separation.
- the halon purification method according to the present embodiment can purify a crude halon containing one kind of halon, or can purify a crude halon containing two or more kinds of halon.
- the concentration of bromine molecules in the crude halon is not particularly limited, but the number of moles of bromine molecules in the crude halon is the number of moles of the bromine molecules in the crude halon in consideration of increasing the removal rate of the bromine molecules from the crude halon.
- the number of moles of halon is preferably 1 time or less, more preferably 0.8 times or less, still more preferably 0.5 times or less.
- the concentration of bromine molecules in purified halon is preferably 0.1% by volume or less, and for that purpose.
- the removal rate of bromine molecules from crude halon is preferably 99.90% or more.
- the concentration of hydrogen bromide in the crude halon is not particularly limited, but in consideration of increasing the removal rate of hydrogen bromide from the crude halon, the crude halon
- the number of moles of hydrogen bromide in the crude is preferably 1.5 times or less, more preferably 1 time or less, and further preferably 0.5 times or less the number of moles of halon in crude halon. preferable.
- the absorption liquid is a liquid that can absorb bromine molecules and is not particularly limited as long as it is an aqueous solution containing a metal iodide, but it is said to be highly safe, easy to handle, and suppress the hydrolysis of halon.
- the liquid property is preferably neutral rather than alkaline or acidic, and the pH may be 5 or more and 9 or less, and more preferably 6 or more and 8 or less. Therefore, the absorbing solution needs to be an aqueous solution of a metal iodide which is a reducing agent, but it is preferably an aqueous solution in which only the metal iodide is dissolved in water, and a basic compound such as a metal hydroxide is dissolved. It is preferable not to do so.
- the absorbing liquid may contain other compounds such as additives as long as the liquid property of the absorbing liquid is kept neutral.
- the type of metal iodide is not particularly limited, but at least one selected from alkali metal iodide and alkaline earth metal iodide is preferable.
- the alkali metal iodide include potassium iodide (KI) and sodium iodide (NaI)
- specific examples of the alkaline earth metal iodide include magnesium iodide (MgI 2 ) and calcium iodide (CaI). 2 ), barium iodide (BaI 2 ) can be mentioned.
- potassium iodide is particularly preferable.
- the amount of metal iodide contained in the absorption liquid may be at least the amount that can absorb the entire amount of bromine molecules to be absorbed by the absorption liquid, that is, at least one time the equivalent amount required for the reaction with the bromine molecules. preferable. In order to improve the removal rate of bromine molecules from crude halon, the amount is more preferably 1.5 times or more, more preferably 2 times or more, and 5 times or more the above equivalent amount. Is particularly preferable.
- the concentration of the metal iodide in the absorption liquid is preferably a concentration at which the metal iodide can be dissolved, and a concentration at which the metal bromide and iodine molecules produced by the reaction can be dissolved in the absorption liquid.
- the concentration of the metal iodide in the absorption liquid may be such that at least a part of the metal iodide cannot be dissolved, that is, the absorption liquid may be a slurry in which solid metal iodide is mixed. good. Therefore, the concentration of the metal iodide in the absorption liquid is preferably 0.1 mol / L or more and 9 mol / L or less.
- the absorption of bromine molecules consumes the metal iodide in the absorption liquid, and when the concentration of the metal iodide decreases, the iodine molecules generated by the above reaction become difficult to dissolve in the absorption liquid. As a result, iodine molecules may precipitate from the absorbing liquid, and the members (for example, piping) of the purification processing apparatus may be clogged.
- the concentration of the metal iodide in the absorption liquid during the purification treatment period is preferably maintained at 40% or more, and is maintained at 60% or more, which is the concentration of the metal iodide in the initial absorption liquid before the purification treatment. Is more preferable. More specifically, during the purification treatment period, the concentration of the metal iodide in the absorption liquid is preferably maintained at 0.5 mol / L or more, and more preferably 0.7 mol / L or more. ..
- the crude halon contains a substance other than the bromine molecule that is thought to react with the metal iodide (for example, if the crude halon contains hydrogen bromide (HBr) described later), this bromine molecule
- the amount of metal iodide contained in the absorption liquid shall be at least 1 times the total equivalent of the equivalent required for the reaction with the bromine molecule and the equivalent required for the reaction with the substance other than the bromine molecule. It is preferably 1.5 times or more, more preferably 2 times or more, and particularly preferably 5 times or more.
- any additive may be dissolved or suspended in the absorption liquid and blended.
- potassium iodate (KIO 3 ) or sodium iodate (NaIO 3 ) can be added to the absorption solution as an additive to add odor from crude halon together with bromine molecules.
- Hydrogen bromide can be removed. Hydrogen bromide is removed from the crude halon by the reaction represented by the following reaction formula (2). 6HBr + 5KI + KIO 3 ⁇ 6KBr + 3I 2 + 3H 2 O ⁇ ⁇ ⁇ (2)
- the amount of the additive contained in the absorption liquid is equal to or greater than the amount capable of absorbing the entire amount of hydrogen bromide to be absorbed in the absorption liquid, that is, the odor.
- the amount is preferably 1 times or more the equivalent amount required for the reaction with hydrogen bromide, and in order to improve the removal rate of hydrogen bromide from crude halon, the amount should be 1.5 times or more the above equivalent amount. It is more preferably 3 times or more, and particularly preferably 7 times or more.
- the amount of the additive contained in the absorption liquid is the amount of the absorption liquid contained in the most upstream absorption tower among the plurality of absorption towers connected in series. It is preferable to apply the above.
- the contact step is a step of bringing the absorbing liquid into contact with the crude halon to obtain a mixed liquid containing the crude halon and the absorbing liquid, and to absorb the bromine molecules in the crude halon into the absorbing liquid.
- the halon purification method according to the present embodiment can purify a gaseous crude halon or a liquid crude halon.
- the method of bringing the absorption liquid into contact with the crude halon is not particularly limited, but when the crude halon is in a liquid state, the crude halon is mixed with the absorption liquid, for example, in an absorption tower and dispersed in the liquid.
- the crude halon can be brought into contact with the absorbent. If the crude halon is in liquid form, the crude halon can be transferred by a liquid feed pump.
- the crude halon and the absorbent can be brought into contact with each other by bubbling the crude halon into the absorbing liquid, sprinkling the absorbing liquid on the crude halon with a scrubber, or the like.
- the crude halon is in the form of a gas
- the absorbing liquid is brought into contact with the gaseous crude halon in the contacting step, and the gaseous purified halon is extracted from the mixed solution in the separation step. Is simple and easy.
- the bubbling method include a method of supplying crude furlong into the absorption liquid contained in the absorption tower. If the crude halon is blown into the absorption liquid through a pipe or the like inserted into the absorption liquid, the absorption liquid can be brought into contact with the crude halon. By blowing crude halon into the absorption liquid, a mixed solution containing the crude halon and the absorption liquid can be obtained, and the bromine molecules in the crude halon react with the metal iodide in the absorption liquid to turn the bromine molecules into the absorption liquid. Be absorbed.
- the bromine molecule is removed from the crude halon by the reaction represented by the following reaction formula (1).
- the metal bromide and iodine molecule (I 2 ) produced by the above reaction remain in the absorption liquid, and Halon is sparingly soluble in water, so that it is separated from the absorption liquid in the separation step.
- the number of absorption towers is not particularly limited, and may be one or a plurality. However, in order to improve the removal rate of bromine molecules from crude halon, a plurality of absorption towers are connected in series to make a crude product. It is preferable to adopt a mode in which halon is continuously blown into a plurality of absorption towers.
- the "amount of metal iodide contained in the absorption liquid" described in the above-mentioned "absorption liquid” section is the most upstream side among the plurality of absorption towers connected in series. It is preferable to apply it to the absorption liquid contained in the absorption tower of.
- the piping and the absorption tower to be inserted into the absorption liquid are preferably made of a material that does not easily react with bromine molecules and halon. Examples of such a material include fluororesin and glass.
- a material that does not easily react with bromine molecules and halon include fluororesin and glass.
- the crude halon When purifying a gaseous crude halon, the crude halon may be made gaseous by the vapor pressure of the halon, or may be made gaseous by mixing a diluted gas such as an inert gas.
- a diluted gas such as an inert gas.
- the diluted gas is mixed with the crude halon, for example, the diluted gas is mixed so that 10% by volume or more and 90% by volume or less of the gaseous mixture obtained by mixing the crude halon and the diluted gas becomes the diluted gas. good.
- the type of the inert gas used as the diluting gas is not particularly limited, but for example, nitrogen gas (N 2 ), helium (He), argon (Ar), neon (Ne), krypton (Kr), and the like.
- Xenon (Xe) can be mentioned.
- nitrogen gas, helium, argon, neon, and krypton are preferable, and nitrogen gas and argon are more preferable.
- nitrogen gas and argon are more preferable.
- One of these inert gases may be used alone, or two or more thereof may be used in combination.
- the separation step is a step of separating halon from a mixed solution containing crude halon and an absorbing solution to obtain an absorbing solution and purified halon that have absorbed bromine molecules. Since halon is sparingly soluble in water, it is separated from the absorbed liquid by gas-liquid separation or liquid-liquid separation due to the difference in specific gravity.
- the method for separating halon from the mixture is not particularly limited, but when halon is in the form of a gas, purified halon is separated from the absorption liquid by gas-liquid separation, and is provided, for example, in the upper part of the absorption tower. It is discharged from the absorption tower through the pipe.
- the purified halon is separated from the absorption liquid by liquid-liquid separation, and when the specific gravity of the halon is smaller than that of the absorption liquid, it is absorbed through, for example, a pipe provided at the top of the absorption tower.
- the halon is discharged from the tower and the specific gravity of the halon is larger than that of the absorption liquid, it is discharged from the absorption tower through, for example, a pipe provided at the bottom of the absorption tower.
- the purification processing apparatus of FIG. 1 includes a crude Halon cylinder 1 filled with a crude halon of gas at normal temperature and pressure, an inert gas cylinder 2 filled with an inert gas, and a first absorption tower 11 for purifying the crude halon. And the second absorption tower 13, the crude halon supply pipe 5 connecting the crude halon cylinder 1 and the first absorption tower 11, and the inert gas connecting the inert gas cylinder 2 to the intermediate portion of the crude halon supply pipe 5. It is provided with a supply pipe 6.
- a crude halon supply unit 3 composed of a mass flow controller or the like is provided on the upstream side portion of the crude halon supply pipe 5 (that is, a portion close to the crude halon bomb 1).
- the crude halon of the crude halon bomb 1 is supplied to the first absorption tower 11 via the crude halon supply pipe 5 while the flow rate is controlled by the crude halon supply unit 3.
- the inert gas supply pipe 6 is provided with an inert gas supply unit 4 including a mass flow controller or the like.
- the flow rate of the inert gas of the inert gas cylinder 2 is controlled by the inert gas supply unit 4, and the intermediate portion of the crude halon supply pipe 5 (that is, from the crude halon supply unit 3) is passed through the inert gas supply pipe 6. Is also supplied to the downstream part).
- the crude halon supply unit 3 sends the crude halon gas to the crude halon supply pipe 5, and the inert gas supply unit 4 supplies the inert gas to the inert gas. It is sent out to the crude halon supply pipe 5 via the pipe 6.
- the crude halon gas is diluted with the inert gas in the intermediate portion of the crude halon supply pipe 5, and the diluted crude halon gas is supplied to the first absorption tower 11 via the crude halon supply pipe 5. ..
- the first absorption liquid 12 is housed in the first absorption tower 11, and the bubbling pipe 16 connected to the downstream end of the crude halon supply pipe 5 is inserted into the first absorption liquid 12. There is. Therefore, since the crude halon is supplied into the first absorption liquid 12 of the first absorption tower 11 and comes into contact with the first absorption liquid 12, the crude halon is purified in the first absorption tower 11.
- the first absorption tower 11 is provided with a temperature control device (not shown) that controls the temperature of the first absorption liquid 12.
- the crude halon from which most of the contained bromine molecules were removed by the purification treatment performed in the first absorption tower 11 is gas-liquid separated from the first absorption liquid 12. Then, the separated crude halon reaches a portion in the first absorption tower 11 above the liquid level of the first absorption liquid 12, and connects the upper part of the first absorption tower 11 and the second absorption tower 13. It is sent to the second absorption tower 13 via the connection pipe 17 to be connected.
- the second absorption liquid 14 is housed in the second absorption tower 13, and the downstream end of the connection pipe 17 is inserted into the second absorption liquid 14. Therefore, the crude halon sent from the first absorption tower 11 is supplied into the second absorption liquid 14 of the second absorption tower 13 and comes into contact with the second absorption liquid 14, so that the second absorption tower Further purification treatment of crude halon is carried out in 13.
- the first absorption liquid 12 and the second absorption liquid 14 may be the same type of absorption liquid or different types of absorption liquid.
- the purified halon separates from the second absorption liquid 14 and reaches a portion in the second absorption tower 13 above the liquid level of the second absorption liquid 14.
- An exhaust pipe 18 for exhausting the internal gas is provided in the upper part of the second absorption tower 13, and high-purity refined halon is external from the second absorption tower 13 via the exhaust pipe 18. It is designed to be discharged to.
- the temperature conditions in the contact process are not particularly limited, but the higher the temperature, the faster the reaction for removing bromine molecules, while if the temperature is too high, the members of the purification processing equipment (for example, piping) are corroded. It is preferably 5 ° C. or higher and 80 ° C. or lower, more preferably 10 ° C. or higher and 60 ° C. or lower, and further preferably 20 ° C. or higher and 60 ° C. or lower.
- the temperature condition of the contact step that is, the temperature of the absorbing liquid, can be controlled by, for example, a heating device or a cooling device provided in the absorption tower in which the absorbing liquid is housed.
- the pressure conditions in the contact step are not particularly limited, but are preferably 0 MPa or more and 0.2 MPa or less, more preferably 0.1 MPa or more and 0.2 MPa or less, and normal pressure (0.1 MPa). It is more preferable to do so.
- Example 1 Using a purification treatment apparatus having the same configuration as the purification treatment apparatus shown in FIG. 1, crude dibromodifluoromethane containing dibromodifluoromethane and bromine molecules (corresponding to "crude halon" which is a constituent requirement of the present invention, and the following A purification treatment was carried out to obtain purified dibromodifluoromethane (hereinafter referred to as “purified halon”) by removing bromine molecules from the “crude halon”). The concentration of bromine molecules in the crude halon was measured by an ion chromatograph manufactured by Shimadzu Corporation and found to be 48.0% by volume.
- This purification treatment apparatus is equipped with two absorption towers made of Teflon (registered trademark) PFA (polyfluoroethylene / perfluoroalkoxyethylene copolymer), and each absorption tower has 1 L of the same composition.
- This absorbing solution is an aqueous solution of potassium iodide which is a reducing agent, the concentration of potassium iodide is 1.2 mol / L, and the pH is 7.
- both the first absorption tower on the upstream side and the second absorption tower on the downstream side are equipped with a temperature control device for controlling the temperature of the absorption liquid, and the temperature of the absorption liquid contained in each absorption tower is set. Both are maintained at 25 ° C. (swing width is ⁇ 2.5 ° C.) during the purification process.
- the crude halon filled in the crude halon bomb was sent to the crude halon supply pipe using the mass flow controller (mass flow controller SEC-N112MGMW manufactured by HORIBA, Ltd.) provided in the crude halon supply unit.
- the nitrogen gas filled in the inert gas bomb is used by the mass flow controller (mass flow controller SEC-N112MGMW manufactured by Horiba Seisakusho Co., Ltd.) provided in the inert gas supply unit, and the crude halon is passed through the piping for supplying the inert gas. It was sent to the supply pipe.
- the crude halon and nitrogen gas were mixed in the crude halon supply pipe to dilute the crude halon.
- the mixing ratio is 80% by volume of crude halon and 20% by volume of nitrogen gas.
- the crude halon diluted with nitrogen gas is supplied to the first absorption tower on the upstream side via the crude halon supply pipe, and is brought into contact with the absorption liquid in the first absorption tower to remove the bromine molecules in the crude halon. It was absorbed by the absorbent solution.
- the crude halon from the first absorption tower is supplied to the second absorption tower on the downstream side via the connection pipe, and is brought into contact with the absorption liquid in the second absorption tower to be in the crude halon.
- the bromine molecule was absorbed by the absorbent solution.
- the potassium iodide concentrations of the first and second absorption liquids were both maintained at 0.72 mol / L or more (that is, 60% or more of the initial concentration).
- the gas discharged from the second absorption tower on the downstream side is a mixed gas of purified halon and nitrogen gas
- purified halon was obtained by removing the nitrogen gas from this mixed gas.
- the method for removing the nitrogen gas is not particularly limited, but in this embodiment, the mixed gas is introduced into a cooling trap cooled with dry ice, and the purified halon is liquefied in the cooling trap to mix the gas. Nitrogen gas was removed from the gas to obtain purified halon.
- the concentration of bromine molecules in the purified halon obtained by removing the nitrogen gas from the mixed gas was measured by an ion chromatograph manufactured by Shimadzu Corporation and found to be 0.0188% by volume.
- Example 2 The crude halon was purified in the same manner as in Example 1 except that the type of the absorption liquid contained in the two absorption towers was an aqueous solution of sodium iodide having a concentration of 1.2 mol / L. The pH of this absorbent was 7. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 99.93%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- Example 3 The crude halon was purified in the same manner as in Example 1 except that the type of the absorption liquid contained in the two absorption towers was an aqueous solution of calcium iodide having a concentration of 1.2 mol / L. The pH of this absorbent was 7. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 99.92%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- Example 4 The crude halon was purified in the same manner as in Example 1 except that the type of the absorption liquid contained in the two absorption towers was an aqueous magnesium iodide solution having a concentration of 1.2 mol / L. The pH of this absorbent was 7. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 99.92%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- Example 5 The crude halon was purified in the same manner as in Example 1 except that the concentration of the bromine molecule in the crude halon was 32.6% by volume. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 99.96%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- Example 6 The crude halon was purified in the same manner as in Example 1 except that the concentration of bromine molecules in the crude halon was 11.3% by volume. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 99.97%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- Example 7 Coarse halon in the same manner as in Example 1 except that the temperature during the purification process of the absorption liquid contained in the first absorption tower on the upstream side was maintained at 45 ° C. (swing width is ⁇ 2.5 ° C.). Was purified. The pH of this absorbent was 7. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 99.99%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- Example 8 Coarse halon in the same manner as in Example 1 except that the temperature during the purification process of the absorption liquid contained in the first absorption tower on the upstream side was maintained at 5 ° C. (swing width is ⁇ 2.5 ° C.). Was purified. The pH of this absorbent was 7. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 99.93%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- Example 9 The crude halon was purified in the same manner as in Example 1 except that the crude bromodifluoromethane containing bromodifluoromethane and bromine molecules was used as the crude halon. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 99.96%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- Example 10 The crude halon was purified in the same manner as in Example 1 except that the crude bromotrifluoroethylene containing bromotrifluoroethylene and a bromine molecule was used as the crude halon. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 99.96%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- Example 2 The crude halon was purified in the same manner as in Example 1 except that the type of the absorption liquid contained in the two absorption towers was an aqueous solution of sodium formate (HCOONA) having a concentration of 1.2 mol / L. rice field. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 98.67%, and the removal rate of bromine molecules was lower than that in the case of using the potassium iodide aqueous solution as the absorption liquid.
- HCOONA sodium formate
- Example 3 In the same manner as in Example 1, the crude halon was prepared in the same manner as in Example 1 except that the type of the absorption liquid contained in the two absorption towers was an aqueous urea ((NH 2 ) 2 CO) solution having a concentration of 1.2 mol / L. Purification treatment was performed. The results are shown in Table 1. The removal rate of bromine molecules by the purification treatment was 98.12%, and the removal rate of bromine molecules was lower than that in the case of using the potassium iodide aqueous solution as the absorption liquid.
- Example 11 Crude dibromodifluoromethane containing dibromodifluoromethane, bromine molecules, and hydrogen bromide was used as the crude halon.
- concentration of bromine molecules in the crude halon measured by an ion chromatograph manufactured by Shimadzu Corporation was 32.6% by volume.
- concentration of hydrogen bromide in the crude halon measured by titration using an aqueous solution of sodium hydroxide (NaOH) having a concentration of 0.05 mol / L was 15.4% by volume.
- the type of absorption liquid contained in the first absorption tower was an aqueous solution of potassium iodide and potassium iodate dissolved in water.
- the concentration of potassium iodide in this aqueous solution is 1.2 mol / L, and the concentration of potassium iodate is 0.0934 mol / L.
- the crude halon was purified in the same manner as in Example 1 to remove bromine molecules and hydrogen bromide in the crude halon.
- the results are shown in Tables 1 and 2.
- the removal rate of bromine molecules by the purification treatment was 99.96%, and the bromine molecules could be removed to a low concentration at which almost no corrosiveness was exhibited.
- the concentration of hydrogen bromide in the purified halon measured by titration using a sodium hydroxide aqueous solution having a concentration of 0.05 mol / L was 0.00227% by volume, and the removal rate of hydrogen bromide by the purification treatment was It was 99.99%.
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Abstract
Description
ハロンには、その合成過程や熱分解により、不純物として臭素分子(Br2)が混入している場合があるが、臭素分子は腐食性や毒性を有するため、ハロンから除去することが好ましい。
また、ハロンから臭素分子を除去して精製する別の方法として、ハロンを吸収液に接触させて臭素分子を吸収液に吸収させる液相抽出法がある。特許文献1には有機塩基水溶液を吸収液として用いる技術が提案されており、特許文献2には金属亜硫酸塩及び金属水酸化物の水溶液を吸収液として用いる技術が提案されている。
さらに、液相抽出法は処理量やコスト面で優れた方法ではあるものの、特許文献1、2の技術で用いられる吸収液はアルカリ溶液であるため、取り扱いに危険を伴うおそれがあるという問題があった。さらに、アルカリ溶液を吸収液として用いると、臭素分子の除去効率が不十分となるおそれがあるとともに、アルカリ溶液によってハロンが加水分解を受けるおそれがあった。
本発明は、混入している臭素分子を簡便に、安全に、且つ効率的に除去して高純度のハロンを得ることができるハロン精製方法を提供することを課題とする。
[1] ハロン及び臭素分子を含有する粗製ハロンから前記臭素分子を除去するハロン精製方法であって、
金属ヨウ化物を含有する水溶液からなる吸収液に前記粗製ハロンを接触させて、前記粗製ハロンと前記吸収液を含有する混合液を得る接触工程と、
前記混合液から前記ハロンを分離して、前記臭素分子を吸収した前記吸収液と前記ハロンとを得る分離工程と、
を備えるハロン精製方法。
[3] 前記金属ヨウ化物がヨウ化カリウムである[1]に記載のハロン精製方法。
[4] 前記接触工程においては気体状の前記粗製ハロンを前記吸収液に接触させ、前記分離工程においては前記混合液から気体状の前記ハロンを気液抽出する[1]~[3]のいずれか一項に記載のハロン精製方法。
[6] 前記ハロンの炭素数が1又は2である[1]~[4]のいずれか一項に記載のハロン精製方法。
[8] 前記吸収液がヨウ素酸カリウム又はヨウ素酸ナトリウムをさらに含有する[1]~[7]のいずれか一項に記載のハロン精製方法。
〔粗製ハロン〕
本実施形態に係るハロン精製方法によって精製可能なハロンの種類は特に限定されるものではないが、分離工程において混合液からハロンを分離する際の分離しやすさを考慮すると、水への溶解度が低く沸点が低いハロンが好ましい。すなわち、炭素数が1以上3以下であるハロンが好ましく、炭素数が1又は2であるハロンがより好ましい。
なお、本実施形態に係るハロン精製方法は、1種のハロンを含有する粗製ハロンを精製することも可能であるし、2種以上のハロンを含有する粗製ハロンを精製することも可能である。
吸収液は、臭素分子を吸収できる液であり、金属ヨウ化物を含有する水溶液であれば特に限定されるものではないが、安全性の高さ、取扱いの容易さ、ハロンの加水分解の抑制という観点から、液性がアルカリ性や酸性ではなく中性であることが好ましく、pHは5以上9以下であってよく、6以上8以下であることがより好ましい。よって、吸収液は、還元剤である金属ヨウ化物の水溶液である必要があるが、水に金属ヨウ化物のみを溶解させた水溶液であることが好ましく、金属水酸化物等の塩基性化合物が溶解していないことが好ましい。ただし、吸収液の液性が中性に保たれるならば、吸収液は添加剤等の他の化合物を含有していてもよい。
臭化水素は、下記反応式(2)に示す反応により粗製ハロンから除去される。
6HBr+5KI+KIO3 → 6KBr+3I2+3H2O ・・・(2)
吸収工程において複数の吸収塔を用いる場合には、吸収液に含有される添加剤の量は、直列に連結された複数の吸収塔のうち最も上流側の吸収塔に収容される吸収液に対して適用することが好ましい。
接触工程は、粗製ハロンに吸収液を接触させて、粗製ハロンと吸収液を含有する混合液を得るとともに、粗製ハロン中の臭素分子を吸収液に吸収させる工程である。本実施形態に係るハロン精製方法は、気体状の粗製ハロンを精製することもできるし、液体状の粗製ハロンを精製することもできる。
Br2+2KI → 2KBr+I2 ・・・(1)
上記反応により生成した金属臭化物とヨウ素分子(I2)は吸収液中に残り、ハロンは水に難溶であるため、分離工程において吸収液から分離される。
粗製ハロンの精製に使用した後の吸収液を廃棄する場合には、金属ヨウ化物と臭素分子の反応により発生したヨウ素分子をチオ硫酸ナトリウム(Na2S2O3)等により処理してから廃棄することが望ましい。
分離工程は、粗製ハロンと吸収液を含有する混合液からハロンを分離して、臭素分子を吸収した吸収液と精製ハロンとを得る工程である。ハロンは、水に難溶であるため、比重の違いから気液分離又は液液分離によって吸収液から分離される。
混合液からハロンを分離する方法は特に限定されるものではないが、ハロンが気体状である場合には、気液分離により精製ハロンが吸収液から分離され、例えば、吸収塔の上部に備えられた配管を通って吸収塔から排出される。ハロンが液体状である場合には、液液分離により精製ハロンが吸収液から分離され、ハロンの比重が吸収液よりも小さい場合は、例えば、吸収塔の上部に備えられた配管を通って吸収塔から排出され、ハロンの比重が吸収液よりも大きい場合は、例えば、吸収塔の下部に備えられた配管を通って吸収塔から排出される。
次に、図1を参照しながら、本実施形態に係るハロン精製方法を実施可能な精製処理装置の構成の一例と、該精製処理装置を用いたハロン精製方法の一例を説明する。
図1の精製処理装置は、常温常圧で気体の粗製ハロンが充填された粗製ハロンボンベ1と、不活性ガスが充填された不活性ガスボンベ2と、粗製ハロンの精製を行う第一の吸収塔11及び第二の吸収塔13と、粗製ハロンボンベ1と第一の吸収塔11を接続する粗製ハロン供給用配管5と、不活性ガスボンベ2を粗製ハロン供給用配管5の中間部に接続する不活性ガス供給用配管6と、を備えている。
接触工程における温度条件は特に限定されるものではないが、温度が高い方が臭素分子を除去する反応の速度が高くなる一方で、温度が高すぎると精製処理装置の部材(例えば配管)が腐食するおそれがあるため、5℃以上80℃以下とすることが好ましく、10℃以上60℃以下とすることがより好ましく、20℃以上60℃以下とすることがさらに好ましい。接触工程の温度条件、すなわち吸収液の温度は、例えば、吸収液が収容される吸収塔に備えられた加熱装置又は冷却装置によって制御することができる。
接触工程における圧力条件は特に限定されるものではないが、0MPa以上0.2MPa以下とすることが好ましく、0.1MPa以上0.2MPa以下とすることがより好ましく、常圧(0.1MPa)とすることがさらに好ましい。
〔実施例1〕
図1に示す精製処理装置と同様の構成を有する精製処理装置を用いて、ジブロモジフルオロメタン及び臭素分子を含有する粗製ジブロモジフルオロメタン(本発明の構成要件である「粗製ハロン」に相当し、以下「粗製ハロン」と記す。)中から臭素分子を除去して精製ジブロモジフルオロメタン(以下「精製ハロン」と記す。)を得る精製処理を行った。粗製ハロン中の臭素分子の濃度を、株式会社島津製作所製のイオンクロマトグラフにより測定した結果、48.0体積%であった。
除去率(%)=〔1-[精製ハロン中の臭素分子の濃度]/[粗製ハロン中の臭素分子の濃度]〕×100
結果を表1に示す。精製処理による臭素分子の除去率は99.96%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
2つの吸収塔に収容されている吸収液の種類を、濃度1.2モル/Lのヨウ化ナトリウム水溶液とした点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。この吸収液のpHは7であった。結果を表1に示す。精製処理による臭素分子の除去率は99.93%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
2つの吸収塔に収容されている吸収液の種類を、濃度1.2モル/Lのヨウ化カルシウム水溶液とした点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。この吸収液のpHは7であった。結果を表1に示す。精製処理による臭素分子の除去率は99.92%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
2つの吸収塔に収容されている吸収液の種類を、濃度1.2モル/Lのヨウ化マグネシウム水溶液とした点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。この吸収液のpHは7であった。結果を表1に示す。精製処理による臭素分子の除去率は99.92%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
粗製ハロン中の臭素分子の濃度が32.6体積%である点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。結果を表1に示す。精製処理による臭素分子の除去率は99.96%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
粗製ハロン中の臭素分子の濃度が11.3体積%である点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。結果を表1に示す。精製処理による臭素分子の除去率は99.97%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
上流側の第一の吸収塔に収容された吸収液の精製処理中の温度を45℃(振れ幅は±2.5℃)に維持した点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。この吸収液のpHは7であった。結果を表1に示す。精製処理による臭素分子の除去率は99.99%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
上流側の第一の吸収塔に収容された吸収液の精製処理中の温度を5℃(振れ幅は±2.5℃)に維持した点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。この吸収液のpHは7であった。結果を表1に示す。精製処理による臭素分子の除去率は99.93%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
ブロモジフルオロメタン及び臭素分子を含有する粗製ブロモジフルオロメタンを粗製ハロンとして用いた点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。結果を表1に示す。精製処理による臭素分子の除去率は99.96%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
ブロモトリフルオロエチレン及び臭素分子を含有する粗製ブロモトリフルオロエチレンを粗製ハロンとして用いた点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。結果を表1に示す。精製処理による臭素分子の除去率は99.96%であり、腐食性がほとんど発現しない低濃度まで臭素分子を除去することができた。
2つの吸収塔に収容されている吸収液の種類を、濃度1.2モル/Lの亜硫酸ナトリウム(Na2SO3)水溶液とした点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。結果を表1に示す。精製処理による臭素分子の除去率は98.86%であり、吸収液としてヨウ化カリウム水溶液を用いた場合と比べて、臭素分子の除去率が低かった。
2つの吸収塔に収容されている吸収液の種類を、濃度1.2モル/Lのギ酸ナトリウム(HCOONa)水溶液とした点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。結果を表1に示す。精製処理による臭素分子の除去率は98.67%であり、吸収液としてヨウ化カリウム水溶液を用いた場合と比べて、臭素分子の除去率が低かった。
2つの吸収塔に収容されている吸収液の種類を、濃度1.2モル/Lの尿素((NH2)2CO)水溶液とした点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。結果を表1に示す。精製処理による臭素分子の除去率は98.12%であり、吸収液としてヨウ化カリウム水溶液を用いた場合と比べて、臭素分子の除去率が低かった。
2つの吸収塔に収容されている吸収液の種類を水(H2O)とした点以外は、実施例1と同様にして、粗製ハロンの精製処理を行った。結果を表1に示す。精製処理による臭素分子の除去率は66.30%であり、吸収液としてヨウ化カリウム水溶液を用いた場合と比べて、臭素分子の除去率が低かった。
ジブロモジフルオロメタン、臭素分子、及び臭化水素を含有する粗製ジブロモジフルオロメタンを、粗製ハロンとして用いた。株式会社島津製作所製のイオンクロマトグラフにより測定した粗製ハロン中の臭素分子の濃度は、32.6体積%であった。また、濃度0.05モル/Lの水酸化ナトリウム(NaOH)水溶液を用いた滴定により測定した粗製ハロン中の臭化水素の濃度は、15.4体積%であった。
上記の2点以外は実施例1と同様にして粗製ハロンの精製処理を行い、粗製ハロン中の臭素分子及び臭化水素の除去を行った。
精製処理による臭化水素の除去率を、下記式に従って算出した。
除去率(%)=〔1-[精製ハロン中の臭化水素の濃度]/[粗製ハロン中の臭化水素の濃度]〕×100
2・・・不活性ガスボンベ
3・・・粗製ハロン供給部
4・・・不活性ガス供給部
11・・・第一の吸収塔
12・・・第一の吸収液
13・・・第二の吸収塔
14・・・第二の吸収液
Claims (8)
- ハロン及び臭素分子を含有する粗製ハロンから前記臭素分子を除去するハロン精製方法であって、
金属ヨウ化物を含有する水溶液からなる吸収液に前記粗製ハロンを接触させて、前記粗製ハロンと前記吸収液を含有する混合液を得る接触工程と、
前記混合液から前記ハロンを分離して、前記臭素分子を吸収した前記吸収液と前記ハロンとを得る分離工程と、
を備えるハロン精製方法。 - 前記金属ヨウ化物が、アルカリ金属ヨウ化物及びアルカリ土類金属ヨウ化物から選ばれる少なくとも1種である請求項1に記載のハロン精製方法。
- 前記金属ヨウ化物がヨウ化カリウムである請求項1に記載のハロン精製方法。
- 前記接触工程においては気体状の前記粗製ハロンを前記吸収液に接触させ、前記分離工程においては前記混合液から気体状の前記ハロンを気液抽出する請求項1~3のいずれか一項に記載のハロン精製方法。
- 前記ハロンの炭素数が1以上3以下である請求項1~4のいずれか一項に記載のハロン精製方法。
- 前記ハロンの炭素数が1又は2である請求項1~4のいずれか一項に記載のハロン精製方法。
- 前記ハロンがブロモメタン、トリブロモフルオロメタン、ブロモジフルオロメタン、ジブロモジフルオロメタン、ブロモトリフルオロメタン、ブロモエタン、ジブロモトリフルオロエタン、ジブロモテトラフルオロエタン、トリブロモトリフルオロエタン、ブロモフルオロエチレン、ブロモジフルオロエチレン、及びブロモトリフルオロエチレンのうちの少なくとも1種である請求項1~4のいずれか一項に記載のハロン精製方法。
- 前記吸収液がヨウ素酸カリウム又はヨウ素酸ナトリウムをさらに含有する請求項1~7のいずれか一項に記載のハロン精製方法。
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