WO2012008560A1 - Process for producing supported ruthenium oxides, and process for producing chlorine - Google Patents
Process for producing supported ruthenium oxides, and process for producing chlorine Download PDFInfo
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- WO2012008560A1 WO2012008560A1 PCT/JP2011/066173 JP2011066173W WO2012008560A1 WO 2012008560 A1 WO2012008560 A1 WO 2012008560A1 JP 2011066173 W JP2011066173 W JP 2011066173W WO 2012008560 A1 WO2012008560 A1 WO 2012008560A1
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- WIPO (PCT)
- Prior art keywords
- titania
- ruthenium oxide
- carrier
- supported
- titania carrier
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 84
- 229910001925 ruthenium oxide Inorganic materials 0.000 title claims abstract description 81
- 239000000460 chlorine Substances 0.000 title claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract 4
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 title description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 419
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 81
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 56
- 239000007789 gas Substances 0.000 claims abstract description 49
- 238000001354 calcination Methods 0.000 claims abstract description 38
- 230000001590 oxidative effect Effects 0.000 claims abstract description 35
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 15
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000013112 stability test Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 235000012149 noodles Nutrition 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- -1 siloxane compound Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SUWCFTLKWQKEFZ-UHFFFAOYSA-M azane;ruthenium(3+);chloride Chemical compound N.N.N.N.N.[Cl-].[Ru+3] SUWCFTLKWQKEFZ-UHFFFAOYSA-M 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000010453 quartz Substances 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
- 150000003377 silicon compounds Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/004—Oxides; Hydroxides
Definitions
- the present invention relates to a process for producing a supported ruthenium oxide in which ruthenium oxide is supported on a carrier.
- the present invention also pertains to a process for producing chlorine by oxidizing hydrogen chloride with oxygen by using, as a catalyst, the supported ruthenium oxide produced by the above-described process.
- Patent Documents 1 and 2 disclose a process comprising the following steps: adding an aqueous acetic acid solution dropwise to a solution of a mixture of tetraethyl orthosilicate with titanium tetraisopropoxide to form a white precipitate, drying the white precipitate at 60°C in air, calcining the same at 550°C to obtain titania silica powder, supporting a ruthenium compound on the titania silica powder, and calcining the same in air; and a process comprising the following steps: supporting a ruthenium compound on molded titania, calcining the same, supporting a silicon compound such as an alkoxysilane compound and a siloxane compound, on the calcined product, and calcining the same in air.
- Patent Document 3 discloses a process which comprises the steps of supporting an alkoxysilane compound on molded titania, calcining the same in air to thereby support silica on the molded titania, supporting a ruthenium compound on the same, and then, calcining the same in air.
- This Document also discloses a process which comprises the steps of molding powdery titania having silica supported thereon, supporting a ruthenium compound on the molded titania, and calcining the same in air, wherein a ratio of rutile type titania to total of the rutile type titania and anatase type titania in the powdery titania is 38%, when measured by the X-ray diffraction method.
- Patent Document 1 JP-A-2002-292279
- Patent Document 2 JP-A-2004-074073
- Patent Document 3 JP-A-2008-155199
- the present inventors have made extensive studies on the production of supported ruthenium oxide catalysts and found out that the following process is effective to achieve the above-described objects: that is, the process comprising the steps of supporting a ruthenium compound on a powdery titania carrier, and calcining the same carrier with the ruthenium compound thereon under an atmosphere of an oxidizing gas, wherein the powdery titania carrier comprises titania and silica supported on the titania, and wherein a ratio of rutile type titania to total of the rutile type titania and anatase type titania is 50% or more, when measured by the X-ray diffraction method.
- the present invention provides the following.
- a process for producing a supported ruthenium oxide comprising the steps of supporting a ruthenium compound on a powdery titania carrier, and calcining the powdery
- titania carrier with the ruthenium compound thereon, under an atmosphere of an oxidizing gas, wherein said powdery titania carrier comprises titania and silica supported on the titania, and wherein a ratio of rutile type titania to total of the rutile type titania and anatase type titania in the powdery titania carrier is 50% or more, when
- a supported ruthenium oxide excellent in thermal stability and catalyst lifetime can be produced, and chlorine can be produced by oxidizing hydrogen chloride with oxygen by the use of the above-obtained supported ruthenium oxide as a catalyst.
- powdery titania carrier comprising titania and silica supported on the titania
- the titnia of such a titania carrier may be rutile type titania (i.e., titania having a rutile type crystalline structure), anatase type titania (i.e., titania having an anatase type crystalline structure) or amorphous titania, or a mixture thereof.
- a titania carrier which comprises rutile type titania as a main component is preferably used.
- a titania carrier in which a ratio of rutile type titania (hereinafter optionally referred to as a rutile type titania ratio) to total of the rutile type titania and anatase type titania in the titania carrier is 50% or more. More preferable is a titania carrier in which a ratio of rutile type titania to total of the rutile type titania and anatase type titania in the titania carrier is 70% or more. Still more preferable is a titania carrier in which a ratio of rutile type titania to total of the rutile type titania and anatase type titania in the titania carrier is 90% or more.
- the rutile type titania ratio can be measured by the X-ray diffraction method (hereinafter referred to as the XRD method) and can be calculated by the following equation (1) :
- I R an intensity of a diffraction line indicating plane
- I A an intensity of a diffraction line indicating plane
- the titania carrier to be used in the present invention is powdery, and it comprises titania and silica previously supported thereon, wherein a ratio of rutile type titania is 50% or more.
- a titania carrier may be a commercially available one or may be prepared by a known method.
- the commercially available titania carrier there are exemplified silica-supporting titania powder (STR-100W®) manufactured by Sakai Chemical Industry Co., Ltd., silica-supporting titania powder ( T-100WP®) manufactured by TAYCA CORPORATION, etc.
- This titania carrier may be prepared, for example, according to the method disclosed in JP-A-2006-182896.
- a content of the silica in the above-described titania carrier is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight, which however varies depending on the physical properties of the titania or a content of ruthenium oxide in the resultant supported ruthenium oxide.
- the above-described titania carrier may contain an alkali metal element.
- the alkali metal element there are exemplified sodium, potassium, cesium, etc., while two or more kinds selected therefrom may be used. Above all, sodium is preferably used.
- This alkali metal element may be such one that is contained in any of the above-mentioned commercially available titania carriers, or may be one which is likely to be contained in the titania carrier during the above-described preparation of the titania carrier with the use of a salt of an alkali metal with silicic acid as a raw material for silica, or may be one which is likely to be contained in the titania carrier during the above-described preparation of the titania carrier, by addition of an alkali metal compound separately from a raw material for silica.
- the alkali metal compound halides of alkali metals are preferable. Among them, sodium chloride and potassium chloride are preferable, and sodium chloride is more preferable.
- a content of the alkali metal element is preferably 5% by weight or less, more preferably 2% by weight or less, based on the weight of the titania carrier.
- a total content of these elements is adjusted to fall within the above-specified range based on the weight of the titania carrier.
- a content of the alkali metal element in the titania carrier can be determined, for example, by the inductively-coupled high-frequency plasma atomic emission spectrometry (hereinafter referred to as "ICP analyzing method" ) .
- the titania carrier may be subjected to a heat treatment which may be carried out under an atmosphere of an oxidizing gas, a reducing gas or an inert gas.
- this heat treatment is carried out under an atmosphere of an oxidizing gas.
- the oxidizing gas means a gas which contains an oxidizing substance, e.g., an oxygen-containing gas or the like, of which an oxygen concentration is usually from about 1 to about 30% by volume.
- an oxygen source therefor generally, air or pure oxygen is used, and may be optionally diluted with an inert gas or water vapor. The use of air as the oxidizing gas is particularly preferable.
- the above-described reducing gas means a gas which contains a reducing substance, e.g., a hydrogen-containing gas, a carbon monoxide-containing gas, a hydrocarbon-containing gas or the like.
- a concentration of the reducing substance is usually from about 1 to about 30% by volume, and this concentraion is controlled with, for example, an inert gas or water vapor.
- the use of the hydrogen-containing gas or the carbon monoxide-containing gas as the reducing gas is particularly preferable.
- the above-described inert gas there are exemplified nitrogen, carbon dioxide, helium, argon and the like. Such an inert gas may be optionally diluted with water vapor.
- the use of nitrogen or carbon dioxide as the inert gas is particularly preferable.
- a temperature for the above-described heat treatment, if carried out, is usually from 300 to 1,000°C, preferably from 500 to 900°C.
- ruthenium compound examples include halides such as RuCl 3 and RuBr 3 ; halogeno acid salts such as K 3 RuCl6 and K 2 RuCl6/ oxo acid salts such as K 2 Ru0 4 ; oxyhalides such as Ru 2 OCl 4 , Ru 2 OCl 5 and Ru 2 OCl 6 ; halogeno complexes such as K 2 [RuCls (H 2 0) 4 ] , [RuCl 2 (H 2 0) 4 ] CI, K 2 [Ru 2 OClio] and Cs 2 [Ru 2 OCl 4 ] ; ammine complexes such as [Ru(NH 3 ) 5 H 2 0]C1 2 , [Ru(NH 3 ) 5 Cl]Cl 2 , [Ru (NH 3 ) 6 ] Cl 2 , [Ru (NH 3 ) 6 ] Cl 3 and [Ru (NH 3 ) ⁇ ] Br 3 ; carbonyl complexes such as [Ru(NH
- a ratio of the ruthenium compound to the titania carrier to be used may be appropriately selected so that a weight ratio of the ruthenium oxide/the titania carrier in the resultant supported ruthenium oxide obtained after calcination, as will be described later, will be preferably 0.1/99.9 to 20.0/80.0, more preferably 0.3/99.7 to 10.0/90.0, still more preferably 0.5/99.5 to 5.0/95.0. Too small an amount of the ruthenium oxide is likely to lead to an insufficient catalytic activity, while too large an amount of the ruthenium oxide is likely to be disadvantageous in view of cost-effectiveness.
- a ratio of the ruthenium compound to the titania carrier to be used is so selected that a content of the ruthenium oxide can be preferably from 0.10 to 20 mol, more preferably from 0.20 to 10 mol, per one mole of the silica supported on the titania carrier.
- a molar number of the ruthenium oxide per one mol of the silica is too large, the thermal stability of the supported ruthenium oxide is likely to lower. On the other hand, when it is too small, the catalytic activity of the same is likely to lower.
- a temperature for the treatment is usually from 0 to 100°C, preferably from 0 to 50°C; and a pressure for the treatment is usually from 0.1 to 1 MPa, preferably an atmospheric pressure.
- This contact treatment may be carried out under an atmosphere of air or an inert gas such as nitrogen, helium, argon or carbon dioxide, which may contain water vapor .
- an impregnation or immersion method may be employed.
- the following methods are exemplified as the method for the contact treatment with the use of the above-described aqueous solution: (A) a method of impregnating the titania carrier with the aqueous solution containing the ruthenium compound; and (B) a method of immersing the titania carrier in the aqueous solution containing the ruthenium compound, while the former method (A) is preferable.
- the aqueous solution may contain an acid.
- water to be contained in the aqueous solution water with a high purity such as distilled water, ion- exchange water or super-pure water is preferably used. If the water to be used contains a lot of impurities, such impurities tend to adhere to the resultant catalyst, which may lead to a decrease in the catalytic activity thereof.
- An amount of the water to be used is usually from 1.5 to 8,000 mol, preferably from 3 to 2,500 mol, more preferably from 7 to 1,500 mol, per one mol of the ruthenium compound in the aqueous solution.
- a lower limit of the amount of the water, required to support the ruthenium compound on the titania carrier can be found by subtracting the volume of the ruthenium compound in the aqueous solution for use in the supporting, from the total pore volume of the titania carrier to be used.
- the ruthenium compound may be thus supported on the titania carrier, and then, may be optionally subjected to a reduction treatment as disclosed in, for example, JP-A- 2000-229239, JP-A-2000-254502 , JP-A-2000-281314 or JP-A- 2002-79093.
- the ruthenium compound After being supported on the titania carrier, the ruthenium compound is then calcined under an atmosphere of an oxidizing gas. This calcination converts the supported ruthenium compound into a ruthenium oxide.
- the oxidizing gas is a gas which contains an oxidizing substance, e.g., an oxygen-containing gas. A concentration of oxygen in such a gas is usually from about 1 to about 30% by volume.
- an oxygen source therefor air or pure oxygen is generally used, which may be optionally diluted with an inert gas. In particular, the use of air as the oxidizing gas is preferable.
- a calcining temperature is usually from
- the ruthenium compound may then be dried and calcined under an atmosphere of an oxidizing gas.
- This drying method may be a known method, wherein a temperature for the drying is usually from a room temperature to about 100°C, and a pressure therefor, usually from 0.001 to 1 MPa, preferably an atmospheric pressure.
- This drying may be carried out under an atmosphere of air or an inert gas such as nitrogen, helium, argon or carbon dioxide, which may contain water vapor .
- the supported ruthenium oxide can be produced.
- An oxidation number of ruthenium in the supported ruthenium oxide is usually +4, which indicates ruthenium dioxide (Ru0 2 ) as the ruthenium oxide, while ruthenium with other oxidation number or a ruthenium oxide in other form may be contained in the supported ruthenium oxide.
- the supported ruthenium oxide of the present invention is used preferably as molded articles.
- the following methods are given as a method of obtaining the supported ruthenium oxide in the form of molded articles:
- (A) a method comprising the steps of molding the above- described titania carrier, supporting the ruthenium compound on the molded titania carrier, and calcining the titania carrier with the ruthenium compound thereon under an atmosphere of an oxidizing gas;
- (B) a method comprising the steps of subjecting the titania carrier to the above-described heat treatment, molding the heat-treated titania carrier, supporting the ruthenium compound on the molded titania carrier, and calcining the molded titania carrier with the ruthenium compound thereon under an atmosphere of an oxidizing gas;
- (C) a method comprising the steps of molding the titania carrier, subjecting the molded titania carrier to the heat treatment, supporting the ruthenium compound on the molded titania carrier, and calcining the titania carrier with the ruthenium compound thereon under an atmosphere of an oxidizing gas;
- (E) a method comprising the steps of subjecting the titania carrier to the heat treatment, supporting the ruthenium compound on the titania carrier, molding the titania carrier with the ruthenium compound thereon, and calcining the same under an atmosphere of an oxidizing gas;
- (F) a method comprising the steps of supporting the ruthenium compound on the titania carrier, calcining the titania carrier with the ruthenium compound thereon under an atmosphere of an oxidizing gas, and molding the same;
- (G) a method comprising the steps of subjecting the titania carrier to the heat treatment, supporting the ruthenium compound on the titania carrier, calcining the titania carrier with the ruthenium compound thereon under an atmosphere of an oxidizing gas, and molding the calcined product .
- the molding step is carried out as follows: for example, titania sol, a molding assistant such as an organic binder, and water are kneaded with the titania carrier, the heat-treated titania carrier, the titania carrier with the ruthenium compound thereon, the heat-treated titania carrier with the ruthenium compound thereon, the titania carrier with the ruthenium compound thereon, having undergone the calcining under the atmosphere of the oxidizing gas, or the heat-treated titania carrier with the ruthenium compound thereon, having undergone the calcining under the atmosphere of the oxidizing gas; and the resulting knead mixture is noodlelike extruded, and is then dried and crushed, to thereby obtain the supported ruthenium oxide as molded articles.
- a molding assistant such as an organic binder
- the oxidizing gas is a gas which contains an oxidizing substance, e.g., an oxygen-containing gas, of which a concentration of oxygen is usually from about 1 to about 30% by volume.
- an oxygen source therefor air or pure oxygen is usually used, and may be optionally diluted with an inert gas. The use of air as the oxidizing gas is particularly preferable.
- a temperature for the calcining step subsequent to the molding step is usually from 400 to 900°C, preferably from 500 to 800°C.
- a specific surface area of the molded titania carrier in the method (A) or a specific surface area of the heat- treated-and-molded titania carrier in the method (B) is usually from 5 to 300 m 2 /g, preferably from 5 to 60 m 2 /g.
- a specific surface area of the calcined titania carrier is allowed to fall within the above-specified range.
- a specific surface area of the titania carrier is too large, the titania and the ruthenium oxide in the resultant supported ruthenium oxide are easily calcined, with the result that thermal stability of the resultant supported ruthenium oxide tends to lower.
- a specific surface area of the titania carrier is too small, the ruthenium oxide in the resultant supported ruthenium oxide is hard to be dispersed, with the result that catlytic activity of the resultant supported ruthenium oxide tends to lower.
- This specific surface area can be measured by the nitrogen adsorption method (or the BET method) , and usually, it is measured by the single point BET method.
- the supported ruthenium oxide thus produced is used as a catalyst, and chlorine can be efficiently produced by oxidizing hydrogen chloride with oxygen in the presence of this catalyst.
- a reaction system with the use of a fluidized bed, a fixed bed or a movable bed can be employed as a reaction system therefor, and the use of a fixed-bed reactor of heat insulation type or heat-exchange type is preferred.
- a fixed-bed reactor of heat insulation type either a monotubular fixed-bed reactor or a multitubular fixed-bed reactor may be used, of which the monotubular fixed-bed reactor is preferably used.
- a fixed-bed reactor of heat-exchange type either a monotubular fixed-bed reactor or a multitubular fixed-bed reactor may be used, of which the multitubular fixed-bed reactor is preferably used.
- This oxidation reaction is an equilibrium reaction. When this reaction is carried out at too high a temperature, an equilibrium conversion tends to lower. The reaction is therefore carried out at a relatively low temperature.
- a temperature for the reaction is usually from 100 to 500°C, preferably from 200 to 450°C.
- a pressure for the reaction is usually from about 0.1 to about 5 Pa.
- oxygen source for the reaction air or pure oxygen may be used. While a theoretical molar amount of oxygen relative to hydrogen chloride is 1/4 mol, an amount of oxygen to be practically used is 0.1 to 10 times larger than this theoretical amount.
- a rate of feeding hydrogen chloride is usually from about 10 to about 20, 000 h "1 , in terms of a gas-feeding rate per one L of a catalyst (L/h at 0°C under one atmospheric pressure), i.e., in terms of GHSV.
- the resultant heat-treated product (100 parts by weight) was mixed with an organic binder [65SH-400, manufactured by Shin-Etsu Chemical Co., Ltd.] (2 parts by weight) .
- This knead-mixture was extruded into a noodle with a diameter of 3.0 ⁇ , which was then dried at 60°C for 2 hours and was then crushed into pieces with lengths of from about 3 to about 5 mm as molded articles.
- the molded articles were heated from a room temperature to 600°C in air over 1.7 hours and were then maintained at the same temperature for 3 hours for calcination thereof.
- the solids (20.6 g) were raised in temperature from a room temperature to 300°C over 1.3 hours under a stream of air and were then maintained at the same temperature for 2 hours for calcination thereof.
- supported ruthenium oxide (20.1 g) having a ruthenium oxide content of 1.25% by weight was obtained.
- the molded articles of the supported ruthenium oxide (1.2 g) obtained as above were charged in a quartz reaction tube with an inner diameter of 21 mm.
- a hydrogen chloride gas, an oxygen gas, a chlorine gas and water vapor were fed into the reaction tube at rates of 0.086 mol/hr. (converted into 1.9 L/hr. at 0°C under one atmospheric pressure), 0.075 mol/hr. (converted into 1.7 L/hr. at 0°C under one atmospheric pressure), 0.064 mol/hr. (converted into 1.4 L/hr. at 0°C under one atmospheric pressure) and 0.064 mol/hr. (converted into 1.4 L/hr.
- the catalyst layer was heated to a temperature of from 435 to 440°C to carry out the reaction.
- the reaction was stopped, and the molded articles of the supported ruthenium oxide were cooled, while a nitrogen gas was being fed at a rate of 0.214 mol/hr. (converted into 4.8 L/hr. at 0°C under one atmospheric pressure) .
- This knead mixture was extruded into a noodle with a diameter of 3.0 ⁇ , which was then dried at 60°C for 2 hours and was then crushed into pieces with lengths of from 3 to 5 mm as molded articles.
- the molded articles were raised in temperature from a room temperature to 600°C in air over 1.7 hours, and were then maintained at the same temperature for 3 hours for calcination thereof.
- an organic binder YB-152A manufactured by YUKEN INDUSTRY CO., LTD.
- This knead mixture was extruded into a noodle with a diameter of 3.0 mm ⁇ t> , which was then dried at 60°C for 2 hours and was then crushed into pieces with lengths of from 3 to 5 mm as molded articles.
- the molded articles were raised in temperature from a room temperature to 600°C in air over 1.7 hours, and were then maintained at the same temperature for 3 hours for calcination thereof.
- the calcined products (20.0 g) obtained as above were impregnated with a solution of tetraethyl orthosilicate [Si(OC 2 H 5 ) 4 manufactured by Wako Pure Chemical Industries, Ltd.] (0.36 g) in ethanol (2.90 g) and was then dried at 24°C for 15 hours under an atmosphere of air.
- the resultant solids (20.1 g) were raised in temperature from a room temperature to 300°C over 0.8 hour under a stream of air and were then maintained at the same temperature for calcination thereof.
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