WO2022158741A1 - 염화수소 산화반응을 통한 염소의 고수율 제조방법 - Google Patents
염화수소 산화반응을 통한 염소의 고수율 제조방법 Download PDFInfo
- Publication number
- WO2022158741A1 WO2022158741A1 PCT/KR2021/019964 KR2021019964W WO2022158741A1 WO 2022158741 A1 WO2022158741 A1 WO 2022158741A1 KR 2021019964 W KR2021019964 W KR 2021019964W WO 2022158741 A1 WO2022158741 A1 WO 2022158741A1
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- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen chloride
- oxidation reaction
- weight
- catalyst
- carrier
- Prior art date
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 87
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 87
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 80
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000460 chlorine Substances 0.000 title claims abstract description 60
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 38
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 41
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 33
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims description 31
- 150000004706 metal oxides Chemical class 0.000 claims description 31
- 238000000465 moulding Methods 0.000 claims description 30
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000008188 pellet Substances 0.000 claims description 12
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 12
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000007138 Deacon process reaction Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012695 Ce precursor Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 150000001785 cerium compounds Chemical class 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- GFGLXZFJKQWOAR-UHFFFAOYSA-J O.[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4] Chemical compound O.[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4] GFGLXZFJKQWOAR-UHFFFAOYSA-J 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- KQJQGYQIHVYKTF-UHFFFAOYSA-N cerium(3+);trinitrate;hydrate Chemical compound O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KQJQGYQIHVYKTF-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Definitions
- the present invention relates to a method for producing chlorine in a high yield through a hydrogen chloride oxidation reaction, and more particularly, it is characterized in that chlorine is produced in a high yield by performing an oxidation reaction of hydrogen chloride in a mixed gas containing carbon oxide.
- the Deacon process a catalytic vapor phase oxidation reaction of hydrogen chloride developed in 1868 by Henry Deacon, is an eco-friendly and energy-efficient process that regenerates hydrogen chloride, a by-product generated in the production process of polyurethane and polycarbonate, into chlorine.
- the CuO/CuCl 2 catalyst used in the early Deacon process has very low activity and must be carried out at a reaction temperature of 400° C. or higher. There was a problem of low catalyst durability as it was lost afterward.
- Korean Patent Application Laid-Open No. 10-2012-0040701 relates to a method for producing chlorine by vapor phase oxidation with a supported catalyst based on ruthenium, wherein the catalyst carrier has a pore diameter of greater than 50 nm.
- a nanoparticle having a plurality of pores and containing ruthenium and a ruthenium compound as a catalytically active component.
- Korean Patent Application Laid-Open No. 10-2011-0107350 relates to a gas phase reaction catalyst comprising one or more active metals on a support comprising aluminum oxide and having high mechanical stability, wherein the aluminum oxide component of the support is substantially alpha-aluminum. The inclusion of oxides is disclosed.
- Korean Patent Application Laid-Open No. 10-2013-0100282 discloses a catalyst for the production of chlorine by catalytic gas phase oxidation of hydrogen chloride using oxygen comprising calcined tin dioxide as a catalyst and at least one halogen-containing ruthenium compound as a support, and Disclosed is its use.
- the present inventors while studying the hydrogen chloride oxidation reaction as described above, when performing the oxidation reaction of hydrogen chloride in a mixed gas containing carbon oxide, compared to the case of performing the oxidation reaction under oxygen alone, the oxidation reaction of hydrogen chloride It was discovered that chlorine can be produced in high yield with improved activity, thereby completing the present invention.
- the present invention has been devised to solve the problems of the prior art, and to provide a method for producing chlorine capable of producing chlorine in a high yield by performing an oxidation reaction of hydrogen chloride in a mixed gas containing carbon oxide. There is a purpose.
- Another object of the present invention is to provide a method for preparing a molded catalyst for a hydrogen chloride oxidation process.
- one aspect of the present invention is,
- a molding catalyst for the hydrogen chloride oxidation process into a reactor; and adding hydrogen chloride and a mixed gas to the reactor to react; it provides a method for producing chlorine through the oxidation reaction of hydrogen chloride, including, wherein the mixed gas includes oxygen and carbon oxide.
- the content of the mixed gas relative to 100 parts by weight of the hydrogen chloride may be 50 parts by weight to 150 parts by weight.
- the content of the carbon oxide relative to the total 100 parts by weight of the mixed gas may be 0.1 parts by weight to 10 parts by weight.
- the carbon oxide may include at least one selected from carbon monoxide (CO) and carbon dioxide (CO 2 ).
- the weight ratio of carbon monoxide (CO) and carbon dioxide (CO 2 ) may be 1: 1 to 20.
- the molding catalyst for the hydrogen chloride oxidation process includes a carrier; and ruthenium oxide supported on the carrier.
- the carrier may include a carrier selected from the group consisting of alumina, titania, zirconia, and combinations thereof.
- the molding catalyst may further include a metal oxide supported on the carrier, and the metal oxide may include a metal oxide represented by the following formula (1).
- M is Ti, Ce, or Zr.
- the content of the ruthenium oxide may be 1 part by weight to 10 parts by weight, and the content of the metal oxide may be 0.5 parts by weight to 10 parts by weight.
- the molding catalyst may be in a form selected from the group consisting of powders, particles, pellets, and combinations thereof.
- the diameter of the pellets may be 1 mm to 10 mm.
- the yield of chlorine through the method for producing chlorine may have a public yield (STY) calculated by Equation 1 below 1.35 or more.
- Equation 1 the reaction time is 50 hours (hr).
- the molding catalyst may have a public yield (STY) calculated by Equation (1) of 1.45 or more.
- the input flow rate of the hydrogen chloride and the mixed gas may be 50 mL/min to 200 mL/min.
- the reaction of the hydrogen chloride and the mixed gas may be carried out at a temperature of 280 °C to 380 °C.
- a method for preparing a molding catalyst for the hydrogen chloride oxidation process comprising: supporting a metal oxide on a carrier; and supporting the ruthenium precursor on the support on which the metal oxide is supported.
- the manufacturing method of the molding catalyst for the hydrogen chloride oxidation process includes the steps of supporting the ruthenium precursor; Thereafter, drying and calcining the carrier; may further include.
- the drying may be performed at a temperature of 50° C. to 150° C. for 3 hours to 5 hours, and the calcination may be performed at a temperature of 300° C. to 700° C. for 2 hours to 6 hours.
- the oxidation reaction activity of hydrogen chloride is performed by performing the oxidation reaction of hydrogen chloride in a mixed gas containing carbon oxide, compared to the case of performing the oxidation reaction under oxygen alone. This may be improved to enable production of chlorine in high yield.
- the catalyst used for the oxidation reaction solves the sintering phenomenon of ruthenium oxide occurring in the commercial production process of chlorine through the oxidation reaction of hydrogen chloride, so that the initial catalyst activity can be maintained despite long-time catalyst operation.
- the catalyst is provided as a catalyst in the form of pellets in the commercial production process of chlorine through the oxidation reaction of hydrogen chloride, and can provide high mechanical strength so that they are not crushed in the process.
- the catalyst provides high catalytic activity and durability, so that it is not limited by the shape of the reactor, operating conditions, etc., so there is no restriction in use and ease in handling.
- the first aspect of the present application is a first aspect of the present application.
- the mixed gas provides a method for producing chlorine through the oxidation reaction of hydrogen chloride that contains oxygen and carbon oxide.
- the carbon oxide is generally a poisonous material of the catalyst, and may be one of impurities that may exist in the feed during the hydrogen chloride oxidation reaction. That is, when a general catalyst is used in the hydrogen chloride oxidation reaction, the carbon oxide may act as a factor inhibiting the oxidation reaction. However, when the molding catalyst for the hydrogen chloride oxidation process according to the present invention is used, carbon oxides, which may act as impurities in the hydrogen chloride oxidation reaction, may rather act as additives that can increase the yield of chlorine.
- the method for producing chlorine through the oxidation reaction of hydrogen chloride may include a step of charging a molding catalyst for the hydrogen chloride oxidation reaction process in a reactor.
- the molded catalyst for the hydrogen chloride oxidation process includes a carrier; and ruthenium oxide supported on the carrier.
- the carrier may include a carrier selected from the group consisting of alumina, titania, zirconia, and combinations thereof, and may preferably include titania.
- the titania carrier may be, for example, anatase-type titania or rutile-type titania, amorphous titania, or a mixture thereof.
- the titania carrier may include an oxide such as alumina, zirconia or niobium oxide.
- a rutile-type titania is provided, for example, titania manufactured by Sakai Corporation may be provided, but is not limited thereto.
- the specific surface area of the titania carrier may be measured by a commonly used BET method, and the specific surface area may be 5 to 300 m 2 /g, preferably 5 to 50 m 2 /g. If the specific surface area exceeds the above range, it may be difficult to secure thermal stability of ruthenium oxide, and if it is less than the above range, there may be problems in which dispersion stability and catalytic activity are lowered.
- the aluminum carrier may preferably be one provided with alpha-alumina.
- the alpha-alumina since the alpha-alumina has a low BET specific surface area, it may be preferable in that absorption of other impurities is difficult to occur.
- the specific surface area of the aluminum carrier may be 10 to 500 m 2 /g, preferably 20 to 350 m 2 /g.
- the zirconia carrier has pores in the range of 0.05 to 10 ⁇ m, and the specific surface area may be the same as the above.
- the molding catalyst may further include a metal oxide supported on the support, and the metal oxide may include a metal oxide represented by the following formula (1).
- M may be Ti, Ce, or Zr. That is, the metal oxide may be titania (TiO 2 ), ceria (CeO 2 ), or zirconia (ZrO 2 ), and may include a metal oxide selected from the group consisting of combinations thereof.
- the metal oxide may be preferably ceria and zirconia, and the weight content ratio of ceria and zirconia may be 1: 0.5 to 1, preferably 1: 1. have.
- the weight content ratio of ceria and zirconia satisfies the above values, the molded catalyst for the hydrogen chloride oxidation process including the same has excellent mechanical strength and catalyst durability and may be suitable for long-term catalyst operation.
- the metal oxide may be provided in the form of a precursor thereof.
- the cerium precursor may exist in the form of a complex salt, and may include a cerium compound, particularly metal salts such as cerium nitrate, cerium acetate, or cerium chloride.
- it may contain cerium nitrate, and after being impregnated in a carrier in the form of a precursor, it may be provided as a final molding catalyst through drying and firing steps.
- the content of the ruthenium oxide may be 1 part by weight to 10 parts by weight, and the content of the metal oxide may be 0.5 parts by weight to 10 parts by weight.
- the molding catalyst may be in a form selected from the group consisting of powders, particles, pellets, and combinations thereof, preferably in the form of pellets.
- the diameter of the pellets may be 1 mm to 10 mm.
- the method for producing chlorine through the oxidation reaction of hydrogen chloride may include a step of reacting by introducing hydrogen chloride and a mixed gas into the reactor.
- the carbon oxide may include at least one selected from carbon monoxide (CO) and carbon dioxide (CO 2 ).
- the carbon oxide may be carbon monoxide (CO) alone, and when both carbon monoxide (CO) and carbon dioxide (CO 2 ) are used, the weight ratio thereof may be 1: 1 to 20.
- the weight ratio of carbon monoxide (CO) and carbon dioxide (CO 2 ) may be about 1: 6 to 7.
- the content of the mixed gas relative to 100 parts by weight of hydrogen chloride may be 50 parts by weight to 150 parts by weight, and according to an embodiment of the present invention, it may be about 100 parts by weight.
- the mixed gas may include coral and carbon oxide, and the content of the carbon oxide relative to 100 parts by weight of the total mixed gas may be 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight. may be negative, and according to an embodiment of the present invention may be 1 to 4 parts by weight.
- the content of the carbon oxide is less than 0.1 parts by weight based on 100 parts by weight of the total mixed gas, it may not be possible to produce chlorine in high yield unique to the present invention according to the input of carbon oxide, and if it exceeds 10 parts by weight, rather carbon oxide is an impurity It may act as a catalyst to reduce the performance of the catalyst.
- the reaction for the production of chlorine may be a fixed bed method or a fluidized bed method, a gas phase reaction, etc. may be provided, and preferably a gas phase reaction may be provided. Since the hydrogen chloride oxidation reaction is an equilibrium reaction and the equilibrium conversion rate is lowered when it is performed at too high a temperature, it is preferably performed at a relatively low temperature. At this time, the reaction temperature may be usually 100 °C to 500 °C, preferably 280 °C to 380 °C. In addition, the reaction pressure may be about 0.1 Mpa to about 5 Mpa.
- the hydrogen chloride supply rate may be expressed as a gas supply rate per 1 L of the catalyst (L/h; 0° C., converted to 1 atm), that is, GHSV, and may be usually about 10 to 20000 h ⁇ 1 .
- the amount of the catalyst input may be slightly modified depending on the temperature, the amount of the catalyst, and the amount of the chlorine product to be produced.
- the input flow rate of the hydrogen chloride and the mixed gas may be 50 mL/min to 200 mL/min, and according to an embodiment of the present invention may be about 100 mL/min.
- the yield of chlorine through the method for producing chlorine may have a publicly available yield (STY) calculated by Equation 1 below 1.35 or more, preferably 1.45 or more.
- the reaction time may be 50 hours (hr). That is, in the method for producing chlorine, since the reaction is performed in a mixed gas containing carbon oxide, the standard yield (STY) may have a high value, and the chlorine produced through this may be obtained in a high yield. may be confirmed.
- a method for preparing a molded catalyst for a hydrogen chloride oxidation process comprising: supporting a metal oxide on a carrier; and supporting the ruthenium precursor on the support on which the metal oxide is supported.
- the method for preparing a molding catalyst for the hydrogen chloride oxidation reaction process may include a step of molding the carrier before supporting the metal oxide.
- the carrier may include a carrier selected from the group consisting of alumina, titania, zirconia, and combinations thereof, and may preferably include titania.
- the molding of the carrier may be performed by mixing the carrier with an organic binder, an inorganic binder, and water.
- the carrier molded as described above may be applicable to a fixed-bed reactor, and may be easily handled without restrictions on use regardless of the shape of the reactor, operating conditions, and the like. In particular, when applied to a fixed bed reactor, it may be used without generating a differential pressure, and may provide improved durability and mechanical strength by increasing catalytic activity and enhancing thermal stability.
- the organic binder is methyl cellulose, hydroxyethyl cellulose, sodium carboxymethyl cellulose, purified starch, dextrin, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyethylene glycol, paraffin, It may include a material selected from the group consisting of a wax emulsion, microcrystalline wax, and combinations thereof, and the moldability of the carrier may be improved by including the organic binder.
- the inorganic binder is a material selected from the group consisting of alumina sol, silica sol, titania sol, zirconia sol, and combinations thereof. may include, and the mechanical properties of the carrier may be improved by including the inorganic binder.
- the method for preparing a molded catalyst for the hydrogen chloride oxidation process may include a step of supporting a metal oxide on a carrier.
- the metal oxide may include a metal oxide represented by the following formula (1).
- M may be Ti, Ce, or Zr. That is, the metal oxide may be titania (TiO 2 ), ceria (CeO 2 ), or zirconia (ZrO 2 ), and may include a metal oxide selected from the group consisting of combinations thereof.
- the metal oxide may be provided in the form of a precursor thereof.
- the cerium precursor may exist in the form of a complex salt, and may include a cerium compound, particularly metal salts such as cerium nitrate, cerium acetate, or cerium chloride.
- it may contain cerium nitrate, and after being impregnated in a carrier in the form of a precursor, it may be provided as a final molding catalyst through drying and firing steps.
- the method for preparing a molding catalyst for the hydrogen chloride oxidation process may include a step of supporting a ruthenium precursor on the support on which the metal oxide is supported.
- the ruthenium precursor may be preferably provided as a halide, and most preferably as ruthenium chloride containing a chloride.
- the ruthenium precursor may be provided as a hydrate of the ruthenium precursor in some cases.
- the ruthenium precursor may be mixed in a solvent in the form of a powder, and a solid carrier is suspended in the solvent to form a precipitate, and the ruthenium precursor is deposited and supported on the solid carrier.
- the temperature provided during the immersion is 0° C. to 100° C., preferably 0° C. to 50° C., and the pressure may be provided at 0.1 Mpa to 1 Mpa, preferably atmospheric pressure.
- the loading may be performed under an air atmosphere or an inert gas atmosphere such as nitrogen, helium, argon, or carbon dioxide, and in this case, may include water vapor. Preferably, it may be carried out under an inert gas atmosphere.
- the solvent in which the ruthenium precursor is dissolved may include a solvent selected from the group consisting of water, alcohol, nitrile, and combinations thereof.
- the water may be distilled water, ion-exchange water, or high-purity water such as ultrapure water (DIW) used.
- the organic solvent may be a monoalcohol, and may be a C3 or higher primary alcohol.
- a C3 alcohol-based organic solvent may be used, and most preferably 1-propanol may be used.
- the solvent can support the ruthenium component only on the outer surface of the titania carrier in which a hydroxy group (-OH) exists by utilizing high wettability and hydrophobicity, It may be to provide an effect of improving the degree of dispersion.
- the content of the solvent is not significantly limited, but if it is excessively large, it takes a lot of drying time, so it may be freely adjusted at the level of a person skilled in the art.
- the method for preparing a molded catalyst for the hydrogen chloride oxidation process comprises: molding the carrier; supporting the metal oxide; and/or supporting a ruthenium precursor on a carrier; Thereafter, drying and calcining the carrier, respectively; may be further included.
- the carrier may be completed as a final molded carrier by performing drying and firing.
- the drying and firing may be alternatively performed as needed, and the order or number of times may be freely adjustable.
- the drying may be performed at a temperature of 50 ° C. to 150 ° C. for 3 hours to 5 hours.
- the drying may be performed through rotation and stirring, and specifically, may be performed by vibrating a drying container or using a stirrer provided in the container.
- the drying temperature may be usually about room temperature to 100 °C
- the pressure is 0.1 to 1 MPa is usually applied, preferably atmospheric pressure may be provided.
- the sintering may be performed at a temperature of 300° C. to 700° C. for 2 hours to 6 hours, and then cooled to room temperature.
- the oxidizing gas provided for the firing may be, for example, a gas containing oxygen.
- the oxygen concentration may be provided in the range of 1 to 30% by volume that is usually applied.
- air or pure oxygen may be generally provided, and an inert gas or water vapor may be further included if necessary.
- the oxidizing gas may preferably be provided with air, and may be cooled to room temperature after firing at a temperature of about 350° C. and 3 hours in an electric furnace under a flow of air.
- a precursor solution obtained by dissolving 0.8 g of ruthenium chloride hydrate (KOJIMA) in 6.0 g of DIW was impregnated in 20 g of the obtained molded carrier, and then dried in an oven at 100° C. for 4 hours.
- the dried molding carrier was calcined in an electric furnace at 350° C. for 3 hours to obtain a molding catalyst having a ruthenium oxide content of 2.6%, a ceria content of 2.5%, and a zirconia content of 2.5%.
- Chlorine was prepared in the same manner as in Example 1, except that the composition of the mixed gas was 2 wt% CO / 98 wt% O 2 .
- Chlorine was prepared in the same manner as in Example 1, except that the composition of the mixed gas was 0.4 wt% CO / 2.6 wt% CO 2 / 97 wt% O 2 .
- Chlorine was prepared in the same manner as in Example 1, except that the composition of the mixed gas was 100 wt% O 2 .
- Example 1 1.47
- Example 2 1.63
- Example 3 1.37 comparative example 1.32
- the oxidation reaction activity of hydrogen chloride is performed by performing the oxidation reaction of hydrogen chloride in a mixed gas containing carbon oxide, compared to the case of performing the oxidation reaction under oxygen alone. This may be improved to enable production of chlorine in high yield.
- the catalyst used for the oxidation reaction solves the sintering phenomenon of ruthenium oxide occurring in the commercial production process of chlorine through the oxidation reaction of hydrogen chloride, so that the initial catalyst activity can be maintained despite long-time catalyst operation.
- the catalyst is provided as a catalyst in the form of pellets in the commercial production process of chlorine through the oxidation reaction of hydrogen chloride, and can provide high mechanical strength so that they are not crushed in the process.
- the catalyst provides high catalytic activity and durability, so that it is not restricted by the shape of the reactor, operating conditions, etc., so there is no restriction in use and ease in handling.
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Abstract
Description
구분 |
공시수득량
(g-Cl2/g-cat h) |
실시예 1 | 1.47 |
실시예 2 | 1.63 |
실시예 3 | 1.37 |
비교예 | 1.32 |
Claims (15)
- 염화수소 산화반응 공정용 성형촉매를 반응기에 충전시키는 단계; 및상기 반응기에 염화수소 및 혼합가스를 투입하여 반응시키는 단계;를 포함하고,상기 혼합가스는 산소 및 탄소산화물을 포함하는 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제1항에 있어서,상기 염화수소 100 중량부 대비 상기 혼합가스의 함량은 50 중량부 내지 150 중량부인 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제1항에 있어서,상기 혼합가스 전체 100 중량부 대비 상기 탄소산화물의 함량은 0.1 중량부 내지 10 중량부인 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제1항에 있어서,상기 탄소산화물은 일산화탄소(CO) 및 이산화탄소(CO2)에서 선택되는 적어도 하나 이상을 포함하는 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제4항에 있어서,상기 일산화탄소(CO) 및 이산화탄소(CO2)의 중량비율은 1: 1 내지 20인 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제1항에 있어서,상기 염화수소 산화반응 공정용 성형촉매는,담체; 및상기 담체에 담지된 루테늄 산화물을 포함하는 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제6항에 있어서,상기 담체는 알루미나, 티타니아, 지르코니아 및 이들의 조합들로 이루어진 군으로부터 선택되는 담체를 포함하는 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제6항에 있어서,상기 성형촉매는 상기 담체에 담지된 금속산화물을 더 포함하는 것이고,상기 금속산화물은 하기 화학식 1로 표시되는 금속산화물을 포함하는 것인 염화수소의 산화반응을 통한 염소의 제조방법:[화학식 1]MO2(상기 화학식 1에서, M은 Ti, Ce 또는 Zr이다.)
- 제8항에 있어서,상기 담체 100 중량부에 대하여,상기 루테늄 산화물의 함량은 1 중량부 내지 10 중량부이고,상기 금속산화물의 함량은 0.5 중량부 내지 10 중량부인 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제1항에 있어서,상기 성형촉매는 분말, 입자, 펠렛 및 이들의 조합들로 이루어진 군으로부터 선택되는 형태로 이루어진 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제10항에 있어서,상기 성형촉매가 펠렛 형태일 경우, 상기 펠렛의 직경은 1 mm 내지 10 mm인 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제1항에 있어서,상기 염화수소 및 혼합가스의 반응은 280℃내지 380℃의 온도에서 수행되는 것인 염화수소의 산화반응을 통한 염소의 제조방법.
- 제1항에 따른 염화수소 산화반응 공정용 성형촉매의 제조방법으로서,담체에 금속산화물을 담지시키는 단계; 및상기 금속산화물이 담지된 담체에 루테늄 전구체를 담지키는 단계;를 포함하는 염화수소 산화반응 공정용 성형촉매의 제조방법.
- 제13항에 있어서,상기 염화수소 산화반응 공정용 성형촉매의 제조방법은,상기 루테늄 전구체를 담지시키는 단계; 이후에,상기 담체를 건조 및 소성시키는 단계;를 더 포함하는 것인 염화수소 산화반응 공정용 성형촉매의 제조방법.
- 제14항에 있어서,상기 건조는 50℃내지 150℃의 온도에서 3 시간 내지 5 시간 동안 수행되는 것이고,상기 소성은 300℃내지 700℃의 온도에서 2 시간 내지 6 시간 동안 수행되는 것인 염화수소 산화반응 공정용 성형촉매의 제조방법.
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EP21921498.8A EP4282817A1 (en) | 2021-01-20 | 2021-12-27 | Method for producing chlorine in high yield through hydrogen chloride oxidation reaction |
CN202180091419.0A CN116685555A (zh) | 2021-01-20 | 2021-12-27 | 通过氯化氢的氧化反应以高产率生产氯气的方法 |
US18/261,126 US20240067521A1 (en) | 2021-01-20 | 2021-12-27 | Method for producing chlorine in high yield through hydrogen chloride oxidation reaction |
JP2023543438A JP2024503888A (ja) | 2021-01-20 | 2021-12-27 | 塩化水素酸化反応による塩素の高収率製造方法 |
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KR1020210008011A KR20220105387A (ko) | 2021-01-20 | 2021-01-20 | 염화수소 산화반응을 통한 염소의 고수율 제조방법 |
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KR20130100282A (ko) | 2010-08-25 | 2013-09-10 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | 기체상 산화에 의한 염소 제조를 위한 촉매 및 방법 |
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2021
- 2021-01-20 KR KR1020210008011A patent/KR20220105387A/ko not_active Application Discontinuation
- 2021-12-27 EP EP21921498.8A patent/EP4282817A1/en active Pending
- 2021-12-27 US US18/261,126 patent/US20240067521A1/en active Pending
- 2021-12-27 WO PCT/KR2021/019964 patent/WO2022158741A1/ko active Application Filing
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JP2007021484A (ja) * | 2005-06-13 | 2007-02-01 | Sumitomo Chemical Co Ltd | 酸化用触媒の製造方法、塩素の製造方法、並びに一酸化炭素及び/又は不飽和炭化水素の酸化方法 |
JP2007144392A (ja) * | 2005-10-28 | 2007-06-14 | Sumitomo Chemical Co Ltd | 酸化用触媒の製造方法、塩素の製造方法、並びに一酸化炭素及び/又は不飽和炭化水素の酸化方法 |
JP2009537451A (ja) * | 2006-05-23 | 2009-10-29 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | 塩化水素含有ガスを酸化する方法 |
JP2010105858A (ja) * | 2008-10-30 | 2010-05-13 | Sumitomo Chemical Co Ltd | 塩素の製造方法、並びに一酸化炭素および/または不飽和炭化水素の酸化方法 |
KR20110107350A (ko) | 2008-12-30 | 2011-09-30 | 바스프 에스이 | 루테늄 및 니켈을 포함하는 염화수소 산화 촉매 |
KR20120040701A (ko) | 2009-07-25 | 2012-04-27 | 바이엘 머티리얼사이언스 아게 | 나노구조화된 루테늄 담체 촉매 상에서의 기상 산화에 의한 염소의 생성 방법 |
KR20130100282A (ko) | 2010-08-25 | 2013-09-10 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | 기체상 산화에 의한 염소 제조를 위한 촉매 및 방법 |
JP2012062235A (ja) * | 2010-09-17 | 2012-03-29 | Mitsui Chemicals Inc | 塩素の製造方法 |
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US20240067521A1 (en) | 2024-02-29 |
JP2024503888A (ja) | 2024-01-29 |
CN116685555A (zh) | 2023-09-01 |
KR20220105387A (ko) | 2022-07-27 |
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