WO2012133149A1 - Method for direct production of hydrogen peroxide using brookite type titanium oxide - Google Patents
Method for direct production of hydrogen peroxide using brookite type titanium oxide Download PDFInfo
- Publication number
- WO2012133149A1 WO2012133149A1 PCT/JP2012/057454 JP2012057454W WO2012133149A1 WO 2012133149 A1 WO2012133149 A1 WO 2012133149A1 JP 2012057454 W JP2012057454 W JP 2012057454W WO 2012133149 A1 WO2012133149 A1 WO 2012133149A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen peroxide
- catalyst
- directly producing
- producing hydrogen
- titanium oxide
- Prior art date
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 159
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000010931 gold Substances 0.000 claims abstract description 21
- 229910052737 gold Inorganic materials 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 31
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 235000010215 titanium dioxide Nutrition 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 101150003085 Pdcl gene Proteins 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 4
- 150000004056 anthraquinones Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 pulp Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/029—Preparation from hydrogen and oxygen
-
- 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
- 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
- B01J23/44—Palladium
-
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J23/42—Platinum
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
Definitions
- the present invention relates to a method for producing hydrogen peroxide by directly reacting hydrogen and oxygen, and more particularly, a method for producing hydrogen peroxide directly using a catalyst containing brookite-type titanium oxide and a specific active metal. About.
- hydrogen peroxide Since hydrogen peroxide has an oxidizing power and a strong bleaching and sterilizing action, it is used as a bleaching and sterilizing agent for paper, pulp, fiber, processed fishery products and the like. In addition, it is an important industrial product widely used for oxidation reactions including epoxidation and hydroxylation. Furthermore, hydrogen peroxide is used for surface cleaning in the semiconductor industry, for chemical polishing of copper, tin and other copper alloy surfaces, for etching electronic circuits, and the like. And since hydrogen peroxide is only water and oxygen even if it decomposes, it is positioned as important from the viewpoint of green chemistry, and has attracted attention as an alternative material for chlorine bleach.
- hydrogen peroxide is produced by an organic method, an anthraquinone method, an electrolysis method or the like, and an anthraquinone method is used as an industrial production method.
- the anthraquinone method has a number of steps such as reduction, oxidation of the anthraquinone medium, extraction of the generated hydrogen peroxide, purification, concentration, etc., and the capital investment cost is high.
- There are environmental problems such as use and release of organic solvents into the atmosphere.
- Patent Document 4 in a method for producing hydrogen peroxide from oxygen and hydrogen under pressure in a sulfuric acid aqueous solution using a platinum group catalyst, by allowing halogen ions such as bromide ions to coexist in the aqueous solution, This shows that high concentration hydrogen peroxide can be selectively produced. That is, in the conventional technique, in order to obtain hydrogen peroxide with a high selectivity in a method for producing hydrogen peroxide with high concentration by catalytically reacting oxygen and hydrogen in a reaction medium, 2 MPa or more. It was necessary to carry out the reaction under high pressure.
- Patent Document 6 discloses a high concentration peroxidation under low pressure by catalytically reacting oxygen and hydrogen using an aqueous solution as a reaction medium on a catalyst in which titania and a platinum group metal are supported on a carrier that is difficult to crush.
- a method for producing hydrogen peroxide that makes it possible to obtain hydrogen.
- Patent Document 7 discloses a suspension obtained by suspending a titanium-containing silicate porous body in a solution (metal salt-containing solution) in which a Pd salt and an Au salt are dissolved, and preparing a suspension.
- a method for producing a catalyst is described in which a liquid is irradiated with ultraviolet rays to deposit metal fine particles containing an alloy of Pd and Au on the surface of a titanium-containing porous silicate.
- this method is a method in which a metal is supported on a suspended catalyst by a photoprecipitation method, and the performance of the catalyst is poor because the supported component is not supported in a highly dispersed manner.
- Patent Document 8 as a method for improving a catalyst for producing direct hydrogen peroxide, a catalyst carrier is acid-washed, and gold and / or palladium, conveniently depositing gold and palladium on the washing carrier at the same time, is used as a catalyst. It is described that the precursor is formed and then the catalyst precursor is preferably heat treated at a temperature of 400 ° C. or higher to form a catalyst comprising gold, palladium or gold and palladium particles. And it is described that silica, titania, alumina, ferric oxide, zeolite or activated carbon is used as a carrier.
- the production conditions are water / methanol and water / acetone, which are unsuitable for obtaining a purified hydrogen peroxide final product from an industrial standpoint, and the reaction pressure is as high as 1 MPa or more.
- US Pat. No. 6,057,097 contains at least one metal selected from groups 7 to 11 of the periodic table and is supported on SiO 2 functionalized by acidic groups bonded to the surface of those metals.
- a catalyst for obtaining hydrogen has been proposed, but the reaction pressure is as high as 9.6 MPa, and further, a reaction in a methanol system, and a purification step is required to obtain a final product.
- Patent Document 10 proposes a method for producing hydrogen peroxide including a step of reacting hydrogen and oxygen in a solvent in the presence of a cationic polymer containing a noble metal and a halogen-containing anion. It is a reaction in the medium.
- the present invention has been made based on the background as described above, and can achieve high selectivity and yield even under a low pressure of about 1 atm without using an organic solvent in an aqueous medium.
- An object is to provide a method capable of producing hydrogen peroxide directly and stably from oxygen.
- the present inventors have conducted intensive studies on the relationship between the crystal structure of titanium oxide (titania) and the production rate and selectivity of hydrogen peroxide.
- brookite-type titanium oxide was used as a carrier.
- Hydrogen peroxide was produced by reacting hydrogen and oxygen in the presence of a catalyst supporting at least one active metal selected from the group consisting of platinum, palladium, silver and gold. The inventors have found that the selectivity and yield are improved in a well-balanced manner and have reached the present invention.
- ⁇ 1> A step of reacting hydrogen and oxygen in the presence of a catalyst in which at least one active metal selected from the group consisting of platinum, palladium, silver, and gold is supported on brookite-type titanium oxide.
- This is a direct method for producing hydrogen peroxide.
- ⁇ 2> The method for directly producing hydrogen peroxide according to ⁇ 1>, wherein the weight of the active metal is 0.01 to 10% by weight with respect to the brookite type titanium oxide.
- ⁇ 3> The method for directly producing hydrogen peroxide according to ⁇ 1> or ⁇ 2>, wherein the catalyst is hydrogen-reduced at a temperature of 400 ° C. or higher in advance.
- ⁇ 4> The method for directly producing hydrogen peroxide according to any one of ⁇ 1> to ⁇ 3>, wherein the catalyst is reduced with hydrazine.
- ⁇ 5> The peroxide according to any one of ⁇ 1> to ⁇ 4>, wherein the catalyst further supports one or more selected from the group consisting of ruthenium, rhodium, iridium, and osmium. This is a direct production method of hydrogen.
- ⁇ 6> The method for directly producing hydrogen peroxide according to any one of ⁇ 1> to ⁇ 5>, wherein the active metal is palladium and / or gold.
- ⁇ 7> The method for directly producing hydrogen peroxide according to ⁇ 6>, wherein the active metals are palladium and gold, and the molar ratio of palladium / gold is 0.1 to 10.
- ⁇ 8> The method for directly producing hydrogen peroxide according to any one of ⁇ 1> to ⁇ 7>, wherein the brookite-type titanium oxide has a specific surface area of at least 50 m 2 / g.
- ⁇ 9> The method for directly producing hydrogen peroxide according to any one of ⁇ 1> to ⁇ 8>, wherein hydrogen peroxide is produced in the absence of an organic solvent.
- ⁇ 10> The method for directly producing hydrogen peroxide according to any one of ⁇ 1> to ⁇ 9> above, wherein an inorganic acid selected from hydrogen halide or sulfuric acid is added to the reaction system and reacted.
- ⁇ 11> The method for directly producing hydrogen peroxide according to ⁇ 10>, wherein the addition amount of the inorganic acid is 0.01 to 10% by weight based on the reaction solution.
- a brookite type titanium oxide is used as a catalyst carrier, whereby the reaction rate of hydrogen peroxide, The selectivity and yield can be improved in a well-balanced manner, and a highly concentrated aqueous hydrogen peroxide solution can be obtained in a short reaction time.
- a purification step is not required to obtain a final product.
- FIG. 1 is a diagram showing an X-ray diffraction of a catalyst obtained in Example 1.
- FIG. 2 is a diagram showing an X-ray diffraction of a catalyst obtained in Example 2.
- any brookite type titanium oxide can be used without particular limitation.
- the specific surface area is important as the catalyst carrier, and the brookite type titanium oxide as the catalyst carrier in the present invention preferably has a large specific surface area, preferably 10 m 2 / g or more, particularly preferably 50 m 2 / g or more. preferable. Further, the upper limit of the specific surface area is preferably 150 m 2 / g or less, and more preferably 100 m 2 / g or less.
- the catalyst used in the present invention is one in which at least one active metal selected from the group consisting of platinum, palladium, silver and gold is supported on the above brookite type titanium oxide as a carrier.
- platinum, palladium, silver or gold can be used alone or as a mixture or as an alloy for the active metal.
- one or more selected from the group consisting of ruthenium, osnium, rhodium and iridium can be used as a mixture or alloy as long as the effects of the present invention are not impaired. .
- the active metal it is preferable to use palladium and / or gold as the active metal.
- the molar ratio of palladium / gold varies depending on the dispersion state of the active metal when supported on brookite-type titanium oxide as a carrier, but is preferably 0.1 to 10, and more preferably 1 to 5.
- the active metal supported on the carrier is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight based on the carrier.
- the amount of catalyst used is preferably 1 to 100 g / l, more preferably 5 to 40 g / l, based on the reaction solution.
- a method for supporting the active metal on brookite-type titanium oxide a method in which the titanium oxide is suspended in an aqueous solution in which a metal salt of the active metal is dissolved and then reduced and supported by a reducing agent is also preferably used.
- a reducing agent oxalic acid, hydrazine or formalin can be used, and hydrazine is preferably used.
- an inorganic acid to the reaction system for reaction.
- the amount of inorganic acid added is preferably 0.01 to 10% by weight based on the reaction solution.
- this inorganic acid application of hydrogen halide or sulfuric acid is preferable, and it is preferable to add either or both of them.
- the reaction temperature during the synthesis reaction is preferably from 0 to 100 ° C., particularly preferably from 5 to 50 ° C.
- the pressure of the reaction is not particularly limited, but is preferably atmospheric pressure to 10M Pascal, and particularly preferably atmospheric pressure to 2M Pascal.
- the reaction time is usually 0.1 to 100 hours, preferably 0.5 to 10 hours. This reaction can be carried out either batchwise or continuously. Further, the flow rates of the hydrogen gas and oxygen gas as raw materials are preferably such that the explosion range is avoided and oxygen is excessive with respect to hydrogen.
- the hydrogen reaction rate is preferably 30% or more, and more preferably 40% or more.
- the selectivity for hydrogen peroxide is preferably 40% or more, and more preferably 60% or more.
- the yield of hydrogen peroxide is preferably 25% or more.
- Example 1 Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g, HAuCl 4 0.05 g and PdCl 2 0.12 g were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 ⁇ 10 ⁇ 4 mol / ml) was added until pH 10 and then a 3% aqueous hydrazine solution was added dropwise. When the color change ceased, the end of the reduction was judged, and the water was removed by heating until it became semi-liquid while stirring with a magnetic stirrer. Further, after removing the magnetic stirrer, the magnetic stirrer was dried overnight in a 85 ° C. dryer.
- NaOH 2.5 ⁇ 10 ⁇ 4 mol / ml
- the dried sample was sized to 0.5 to 1.8 mm and subjected to reduction treatment for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst.
- the obtained catalyst was examined for X-ray diffraction. The result is shown in FIG.
- Example 2 (Evaporation to dryness method) Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g, HAuCl 4 0.05 g and PdCl 2 0.12 g were suspended in 100 ml of water. While stirring with a magnetic stirrer, the water was removed by heating until it became semi-liquid. Furthermore, after removing the magnetic stirrer, it was dried at 60 ° C. overnight. The dried sample was pulverized, sized to 0.5 to 1.18 mm, and reduced for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst. The obtained catalyst was examined for X-ray diffraction. The result is shown in FIG. Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
- Example 3 Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g, HAuCl 4 0.086 g and PdCl 2 0.203 g were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 ⁇ 10 ⁇ 4 mol / ml) was added until pH 10 and 3% aqueous hydrazine solution was added dropwise. When the color change ceased, the end of the reduction was judged, and the water was removed by heating until it became semi-liquid while stirring with a magnetic stirrer. Further, after removing the magnetic stirrer, the magnetic stirrer was dried overnight in an 85 ° C. dryer. The dried sample was sized to 0.5 to 1.8 mm to obtain a granular catalyst. Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
- Example 4 Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g and PdCl 2 0.203 g were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 ⁇ 10 ⁇ 4 mol / ml) was added until pH 10 and 3% aqueous hydrazine solution was added dropwise. When the color change ceased, the end of the reduction was judged, and the water was removed by heating until it became semi-liquid while stirring with a magnetic stirrer. Further, after removing the magnetic stirrer, the magnetic stirrer was dried overnight in an 85 ° C. dryer. The dried sample was sized to 0.5 to 1.8 mm to obtain a granular catalyst. Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
- Example 5 Showa Denko high surface area brookite type titania (specific surface area 74m 2 / g) 10g, PdCl 2 0.203g and Pt (NH 3 ) 4 Cl 2 ⁇ H 2 O 0.22g suspended in 300ml water up to 60 ° C Heated. NaOH (2.5 ⁇ 10 ⁇ 4 mol / ml) was added until pH 10 and 3% aqueous hydrazine solution was added dropwise. When the color change ceased, the end of the reduction was judged, and the water was removed by heating until it became semi-liquid while stirring with a magnetic stirrer. Further, after removing the magnetic stirrer, the magnetic stirrer was dried overnight in an 85 ° C. dryer. The dried sample was sized to 0.5 to 1.8 mm to obtain a granular catalyst. Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
- the dried sample was sized to 0.5 to 1.8 mm and subjected to reduction treatment for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst.
- Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a method for direct production of hydrogen peroxide having a step of reacting hydrogen and oxygen under the presence of a catalyst in which at least one type of active metal selected from the group consisting of platinum, palladium, silver and gold is deposited on a brookite type titanium oxide.
Description
本発明は、水素と酸素を直接反応させて過酸化水素を製造する方法に関し、更に詳しくは、ブルッカイト型の酸化チタンと特定の活性金属とを含有する触媒を用いた過酸化水素の直接製造法に関する。
The present invention relates to a method for producing hydrogen peroxide by directly reacting hydrogen and oxygen, and more particularly, a method for producing hydrogen peroxide directly using a catalyst containing brookite-type titanium oxide and a specific active metal. About.
過酸化水素は、酸化力を有し強力な漂白・殺菌作用を持つことから、紙、パルプ、繊維、水産加工品等の漂白剤、殺菌剤として利用されている。また、エポキシ化及びヒドロキシル化をはじめとする酸化反応に広範囲に用いられる重要な工業製品である。更には半導体産業における表面の清浄に、銅、錫及び他の銅合金表面の化学的研磨に、電子回路の蝕刻等に過酸化水素は用いられる。そして、過酸化水素は分解しても水と酸素にしかならないためグリーンケミストリーの観点から重要な位置付けがなされており、塩素系漂白剤の代替材料としても着目されている。
Since hydrogen peroxide has an oxidizing power and a strong bleaching and sterilizing action, it is used as a bleaching and sterilizing agent for paper, pulp, fiber, processed fishery products and the like. In addition, it is an important industrial product widely used for oxidation reactions including epoxidation and hydroxylation. Furthermore, hydrogen peroxide is used for surface cleaning in the semiconductor industry, for chemical polishing of copper, tin and other copper alloy surfaces, for etching electronic circuits, and the like. And since hydrogen peroxide is only water and oxygen even if it decomposes, it is positioned as important from the viewpoint of green chemistry, and has attracted attention as an alternative material for chlorine bleach.
従来、過酸化水素は、有機法、アントラキノン法、電解法等より製造されており、特に工業的な製造方法としてアントラキノン法が用いられている。しかし、アントラキノン法は、アントラキノン媒体の還元、酸化、生成過酸化水素の抽出、精製、濃縮等といったように多段階からなり、設備投資コストが高くなるという欠点があるのに加え、エネルギーを多量に使用することと、有機溶剤の大気への放出があるなど環境上の問題点がある。
Conventionally, hydrogen peroxide is produced by an organic method, an anthraquinone method, an electrolysis method or the like, and an anthraquinone method is used as an industrial production method. However, the anthraquinone method has a number of steps such as reduction, oxidation of the anthraquinone medium, extraction of the generated hydrogen peroxide, purification, concentration, etc., and the capital investment cost is high. There are environmental problems such as use and release of organic solvents into the atmosphere.
これらの問題点を改善するために、上記製造法以外の製造方法が試みられているが、その一つに、反応媒体中で触媒を用いて、酸素と水素から直接的に過酸化水素を製造する方法がある。例えば、白金族金属を触媒として用い、酸素と水素から過酸化水素を製造する方法が提案されており、ある程度高い濃度の過酸化水素が生成する事が知られている（例えば、特許文献１、特許文献２および特許文献３）。これらでは、いずれも反応圧力が２ＭＰａ以上で、反応媒体として酸や無機塩を溶存させた水溶液を用いている。反応中の選択率の低下を抑制するため、反応媒体中にハロゲンイオンを添加することにより触媒の活性が抑制されて過酸化水素生成反応の選択性が大幅に向上し、取得過酸化水素の濃度が高くなることが示されている。
In order to improve these problems, production methods other than the above production method have been tried. One of them is production of hydrogen peroxide directly from oxygen and hydrogen using a catalyst in a reaction medium. There is a way to do it. For example, a method for producing hydrogen peroxide from oxygen and hydrogen using a platinum group metal as a catalyst has been proposed, and it is known that hydrogen peroxide having a somewhat high concentration is generated (for example, Patent Document 1, Patent Document 2 and Patent Document 3). In these, the reaction pressure is 2 MPa or more, and an aqueous solution in which an acid or an inorganic salt is dissolved is used as a reaction medium. In order to suppress the decrease in selectivity during the reaction, the activity of the catalyst is suppressed by adding halogen ions to the reaction medium, and the selectivity of the hydrogen peroxide generation reaction is greatly improved. Is shown to be higher.
特許文献４には、白金族触媒を用い、硫酸酸性水溶液中で加圧下、酸素及び水素から過酸化水素を製造する方法に於いて、水溶液中に臭化物イオン等のハロゲンイオンを共存させる事によって、選択的に高濃度の過酸化水素を製造出来る事を示している。即ち従来の技術では、酸素と水素を反応媒体中で接触的に反応させて高濃度の過酸化水素を製造する方法に於いて、高い選択率で過酸化水素を取得するためには、２ＭＰａ以上の高圧下で反応を行う必要があった。また、チタニアを担体とする白金族金属触媒を用いた製造方法では、低圧下で、選択率を著しく低下させることなく高濃度の過酸化水素が得られることが示されている（例えば、特許文献５）。しかし、このチタニアは粒子径が小さいものが多く、また粒子形状も粉砕し易いものであるため工業用触媒としての実用化は困難であった。
In Patent Document 4, in a method for producing hydrogen peroxide from oxygen and hydrogen under pressure in a sulfuric acid aqueous solution using a platinum group catalyst, by allowing halogen ions such as bromide ions to coexist in the aqueous solution, This shows that high concentration hydrogen peroxide can be selectively produced. That is, in the conventional technique, in order to obtain hydrogen peroxide with a high selectivity in a method for producing hydrogen peroxide with high concentration by catalytically reacting oxygen and hydrogen in a reaction medium, 2 MPa or more. It was necessary to carry out the reaction under high pressure. In addition, it has been shown that a production method using a platinum group metal catalyst using titania as a carrier can obtain a high concentration of hydrogen peroxide at a low pressure without significantly reducing the selectivity (for example, Patent Documents). 5). However, since many of these titanias have small particle diameters and the particle shapes are easily pulverized, it has been difficult to put them into practical use as industrial catalysts.
一方、特許文献６には、破砕しにくい担体にチタニアと白金族金属を担持した触媒上で、水溶液を反応媒体として酸素と水素を接触的に反応せしめることにより、低圧下で高濃度の過酸化水素を得ることを可能とした過酸化水素の製造方法を提案している。
On the other hand, Patent Document 6 discloses a high concentration peroxidation under low pressure by catalytically reacting oxygen and hydrogen using an aqueous solution as a reaction medium on a catalyst in which titania and a platinum group metal are supported on a carrier that is difficult to crush. We have proposed a method for producing hydrogen peroxide that makes it possible to obtain hydrogen.
更に、特許文献７には、Ｐｄ塩およびＡｕ塩を溶解した溶液（金属塩含有溶液）中に、チタン含有珪酸塩多孔体を懸濁させて、懸濁液を調製し、得られた懸濁液に、紫外線を照射して、チタン含有珪酸塩多孔体の表面に、ＰｄとＡｕとの合金を含む金属微粒子を析出させる、触媒の製造方法が記載されている。但し、この方法は懸濁された触媒に光析出法で金属を担持させる方法であり、担持成分がうまく高分散担持されていないため触媒の性能が悪い。更には、触媒を得るのに非常に長い時間を要するため実際の製造に必要な触媒量を得る方法としては不適である。また、特許文献８には、直接法過酸化水素の製造触媒の改良法として、触媒担体を酸洗浄し、金及び／又はパラジウム、都合よくは同時に金とパラジウムを洗浄担体上に堆積させて触媒前駆体を形成し、その後触媒前駆体を好ましくは４００℃以上の温度で熱処理して、金、パラジウム又は金とパラジウムの粒子を含む触媒を形成させることが記載されている。そして、担体として、シリカ、チタニア、アルミナ、酸化第二鉄、ゼオライト又は活性炭を使用することが記載されている。但し、製造条件としては水／メタノール系、水／アセトン系であり工業的見地からは精製された過酸化水素最終製品を得るのには不適であり、反応圧力も１Mpa以上と高い。
特許文献９には、周期律表のグループ７ないし１１から選択された少なくとも１つの金属を含み、それらの金属の表面に結合された酸性基により機能化されたＳｉＯ２上に支持された過酸化水素を得るための触媒が提案されているが、反応圧力が９．６ＭＰaと非常に高く、更にはメタノール系での反応であり、最終製品を得るには精製工程が必要である。
特許文献10には、貴金属およびハロゲン含有アニオンを含むカチオン性ポリマーの存在下で、溶媒中で水素と酸素を反応させるステップを含む過酸化水素の製造方法が提案されているが、この方法もメタノール媒体中での反応である。 Furthermore, Patent Document 7 discloses a suspension obtained by suspending a titanium-containing silicate porous body in a solution (metal salt-containing solution) in which a Pd salt and an Au salt are dissolved, and preparing a suspension. A method for producing a catalyst is described in which a liquid is irradiated with ultraviolet rays to deposit metal fine particles containing an alloy of Pd and Au on the surface of a titanium-containing porous silicate. However, this method is a method in which a metal is supported on a suspended catalyst by a photoprecipitation method, and the performance of the catalyst is poor because the supported component is not supported in a highly dispersed manner. Furthermore, since a very long time is required to obtain a catalyst, it is not suitable as a method for obtaining a catalyst amount necessary for actual production. Further, in Patent Document 8, as a method for improving a catalyst for producing direct hydrogen peroxide, a catalyst carrier is acid-washed, and gold and / or palladium, conveniently depositing gold and palladium on the washing carrier at the same time, is used as a catalyst. It is described that the precursor is formed and then the catalyst precursor is preferably heat treated at a temperature of 400 ° C. or higher to form a catalyst comprising gold, palladium or gold and palladium particles. And it is described that silica, titania, alumina, ferric oxide, zeolite or activated carbon is used as a carrier. However, the production conditions are water / methanol and water / acetone, which are unsuitable for obtaining a purified hydrogen peroxide final product from an industrial standpoint, and the reaction pressure is as high as 1 MPa or more.
US Pat. No. 6,057,097 contains at least one metal selected from groups 7 to 11 of the periodic table and is supported on SiO 2 functionalized by acidic groups bonded to the surface of those metals. A catalyst for obtaining hydrogen has been proposed, but the reaction pressure is as high as 9.6 MPa, and further, a reaction in a methanol system, and a purification step is required to obtain a final product.
Patent Document 10 proposes a method for producing hydrogen peroxide including a step of reacting hydrogen and oxygen in a solvent in the presence of a cationic polymer containing a noble metal and a halogen-containing anion. It is a reaction in the medium.
特許文献９には、周期律表のグループ７ないし１１から選択された少なくとも１つの金属を含み、それらの金属の表面に結合された酸性基により機能化されたＳｉＯ２上に支持された過酸化水素を得るための触媒が提案されているが、反応圧力が９．６ＭＰaと非常に高く、更にはメタノール系での反応であり、最終製品を得るには精製工程が必要である。
特許文献10には、貴金属およびハロゲン含有アニオンを含むカチオン性ポリマーの存在下で、溶媒中で水素と酸素を反応させるステップを含む過酸化水素の製造方法が提案されているが、この方法もメタノール媒体中での反応である。 Furthermore, Patent Document 7 discloses a suspension obtained by suspending a titanium-containing silicate porous body in a solution (metal salt-containing solution) in which a Pd salt and an Au salt are dissolved, and preparing a suspension. A method for producing a catalyst is described in which a liquid is irradiated with ultraviolet rays to deposit metal fine particles containing an alloy of Pd and Au on the surface of a titanium-containing porous silicate. However, this method is a method in which a metal is supported on a suspended catalyst by a photoprecipitation method, and the performance of the catalyst is poor because the supported component is not supported in a highly dispersed manner. Furthermore, since a very long time is required to obtain a catalyst, it is not suitable as a method for obtaining a catalyst amount necessary for actual production. Further, in Patent Document 8, as a method for improving a catalyst for producing direct hydrogen peroxide, a catalyst carrier is acid-washed, and gold and / or palladium, conveniently depositing gold and palladium on the washing carrier at the same time, is used as a catalyst. It is described that the precursor is formed and then the catalyst precursor is preferably heat treated at a temperature of 400 ° C. or higher to form a catalyst comprising gold, palladium or gold and palladium particles. And it is described that silica, titania, alumina, ferric oxide, zeolite or activated carbon is used as a carrier. However, the production conditions are water / methanol and water / acetone, which are unsuitable for obtaining a purified hydrogen peroxide final product from an industrial standpoint, and the reaction pressure is as high as 1 MPa or more.
US Pat. No. 6,057,097 contains at least one metal selected from groups 7 to 11 of the periodic table and is supported on SiO 2 functionalized by acidic groups bonded to the surface of those metals. A catalyst for obtaining hydrogen has been proposed, but the reaction pressure is as high as 9.6 MPa, and further, a reaction in a methanol system, and a purification step is required to obtain a final product.
かかる過酸化水素の直接製造法では、合成反応の選択性、生成速度等の因子からなる製造効率が重要となる。この点、上記従来法によれば、ある程度の過酸化水素を製造することができる。しかしながら、上記従来の方法では、選択性、生成速度、収率等を総合的に満足させつつ反応を進行させるものではなく、また反応成績を上げるために、高い反応圧力を必要とするもの、更には水／メタノール系及び水／アセントン系の反応溶液を使用しているものもあり、工業的製造に制限を受けるか、経済的に満足できるレベルにまで達していないのが現状である。
In such a direct production method of hydrogen peroxide, production efficiency including factors such as selectivity of synthesis reaction and production rate is important. In this respect, according to the conventional method, a certain amount of hydrogen peroxide can be produced. However, in the above conventional method, the reaction is not allowed to proceed while comprehensively satisfying the selectivity, production rate, yield, etc., and a high reaction pressure is required to improve the reaction results, Some use water / methanol-based and water / asenton-based reaction solutions, and are currently limited to industrial production or have not reached economically satisfactory levels.
本発明は以上のような背景のもとになされたものであり、水媒体中で有機溶媒を使用せず1気圧程度の低い圧力のもとでも高い選択率、収率を達成できる、水素と酸素から過酸化水素を直接的に安定的に製造することができる方法を提供することを目的とする。
The present invention has been made based on the background as described above, and can achieve high selectivity and yield even under a low pressure of about 1 atm without using an organic solvent in an aqueous medium. An object is to provide a method capable of producing hydrogen peroxide directly and stably from oxygen.
本発明者等は、上記課題を解決すべく、酸化チタン（チタニア）の結晶構造と過酸化水素の生成速度および選択率の関係について鋭意検討を行った結果、ブルッカイト型の酸化チタンを担体とし、それに白金、パラジウム、銀及び金からなる群より選択される少なくとも１種の活性金属を担持させた触媒の存在下で、水素と酸素とを反応させて過酸化水素を製造したところ、反応速度、選択率及び収率がバランスよく向上することを見出し本発明に到達した。
In order to solve the above problems, the present inventors have conducted intensive studies on the relationship between the crystal structure of titanium oxide (titania) and the production rate and selectivity of hydrogen peroxide. As a result, brookite-type titanium oxide was used as a carrier. Hydrogen peroxide was produced by reacting hydrogen and oxygen in the presence of a catalyst supporting at least one active metal selected from the group consisting of platinum, palladium, silver and gold. The inventors have found that the selectivity and yield are improved in a well-balanced manner and have reached the present invention.
即ち、上記課題は、以下の本発明によって解決することができる。
＜１＞ ブルッカイト型の酸化チタンに、白金、パラジウム、銀及び金からなる群より選択される少なくとも１種の活性金属を担持させた触媒の存在下で、水素と酸素とを反応させる工程を有する過酸化水素の直接製造法である。
＜２＞ 前記活性金属の重量が、前記ブルッカイト型の酸化チタンに対して０．０１～１０重量％である、上記＜１＞に記載の過酸化水素の直接製造法である。
＜３＞ 前記触媒が、予め４００℃以上の温度で水素還元されたものである、上記＜１＞または＜２＞に記載の過酸化水素の直接製造法である。
＜４＞ 前記触媒が、ヒドラジンによって還元されたものである、上記＜１＞から＜３＞のいずれかに記載の過酸化水素の直接製造法である。
＜５＞ 前記触媒が、更に、ルテニウム、ロジウム、イリジウム及びオスミウムからなる群より選択される１種以上を担持させたものである、上記＜１＞から＜４＞のいずれかに記載の過酸化水素の直接製造法である。
＜６＞ 前記活性金属が、パラジウムおよび／または金である、上記＜１＞から＜５＞のいずれかに記載の過酸化水素の直接製造法である。
＜７＞ 前記活性金属が、パラジウムおよび金であり、パラジウム／金のモル比が０．１～１０である、上記＜６＞に記載の過酸化水素の直接製造法である。
＜８＞ 前記ブルッカイト型の酸化チタンが、少なくとも５０ｍ２／ｇの比表面積を有する、上記＜１＞から＜７＞のいずれかに記載の過酸化水素の直接製造法である。
＜９＞ 有機溶媒の不存在下で過酸化水素を製造する、上記＜１＞から＜８＞のいずれかに記載の過酸化水素の直接製造法である。
＜１０＞
反応系にハロゲン化水素又は硫酸から選択される無機酸を添加して反応させる、上記＜１＞から＜９＞のいずれかに記載の過酸化水素の直接製造法である。
＜１１＞
前記無機酸の添加量が、反応溶液に対して０．０１～１０重量％である、上記＜１０＞に記載の過酸化水素の直接製造法である。 That is, the said subject can be solved by the following this invention.
<1> A step of reacting hydrogen and oxygen in the presence of a catalyst in which at least one active metal selected from the group consisting of platinum, palladium, silver, and gold is supported on brookite-type titanium oxide. This is a direct method for producing hydrogen peroxide.
<2> The method for directly producing hydrogen peroxide according to <1>, wherein the weight of the active metal is 0.01 to 10% by weight with respect to the brookite type titanium oxide.
<3> The method for directly producing hydrogen peroxide according to <1> or <2>, wherein the catalyst is hydrogen-reduced at a temperature of 400 ° C. or higher in advance.
<4> The method for directly producing hydrogen peroxide according to any one of <1> to <3>, wherein the catalyst is reduced with hydrazine.
<5> The peroxide according to any one of <1> to <4>, wherein the catalyst further supports one or more selected from the group consisting of ruthenium, rhodium, iridium, and osmium. This is a direct production method of hydrogen.
<6> The method for directly producing hydrogen peroxide according to any one of <1> to <5>, wherein the active metal is palladium and / or gold.
<7> The method for directly producing hydrogen peroxide according to <6>, wherein the active metals are palladium and gold, and the molar ratio of palladium / gold is 0.1 to 10.
<8> The method for directly producing hydrogen peroxide according to any one of <1> to <7>, wherein the brookite-type titanium oxide has a specific surface area of at least 50 m 2 / g.
<9> The method for directly producing hydrogen peroxide according to any one of <1> to <8>, wherein hydrogen peroxide is produced in the absence of an organic solvent.
<10>
The method for directly producing hydrogen peroxide according to any one of <1> to <9> above, wherein an inorganic acid selected from hydrogen halide or sulfuric acid is added to the reaction system and reacted.
<11>
The method for directly producing hydrogen peroxide according to <10>, wherein the addition amount of the inorganic acid is 0.01 to 10% by weight based on the reaction solution.
＜１＞ ブルッカイト型の酸化チタンに、白金、パラジウム、銀及び金からなる群より選択される少なくとも１種の活性金属を担持させた触媒の存在下で、水素と酸素とを反応させる工程を有する過酸化水素の直接製造法である。
＜２＞ 前記活性金属の重量が、前記ブルッカイト型の酸化チタンに対して０．０１～１０重量％である、上記＜１＞に記載の過酸化水素の直接製造法である。
＜３＞ 前記触媒が、予め４００℃以上の温度で水素還元されたものである、上記＜１＞または＜２＞に記載の過酸化水素の直接製造法である。
＜４＞ 前記触媒が、ヒドラジンによって還元されたものである、上記＜１＞から＜３＞のいずれかに記載の過酸化水素の直接製造法である。
＜５＞ 前記触媒が、更に、ルテニウム、ロジウム、イリジウム及びオスミウムからなる群より選択される１種以上を担持させたものである、上記＜１＞から＜４＞のいずれかに記載の過酸化水素の直接製造法である。
＜６＞ 前記活性金属が、パラジウムおよび／または金である、上記＜１＞から＜５＞のいずれかに記載の過酸化水素の直接製造法である。
＜７＞ 前記活性金属が、パラジウムおよび金であり、パラジウム／金のモル比が０．１～１０である、上記＜６＞に記載の過酸化水素の直接製造法である。
＜８＞ 前記ブルッカイト型の酸化チタンが、少なくとも５０ｍ２／ｇの比表面積を有する、上記＜１＞から＜７＞のいずれかに記載の過酸化水素の直接製造法である。
＜９＞ 有機溶媒の不存在下で過酸化水素を製造する、上記＜１＞から＜８＞のいずれかに記載の過酸化水素の直接製造法である。
＜１０＞
反応系にハロゲン化水素又は硫酸から選択される無機酸を添加して反応させる、上記＜１＞から＜９＞のいずれかに記載の過酸化水素の直接製造法である。
＜１１＞
前記無機酸の添加量が、反応溶液に対して０．０１～１０重量％である、上記＜１０＞に記載の過酸化水素の直接製造法である。 That is, the said subject can be solved by the following this invention.
<1> A step of reacting hydrogen and oxygen in the presence of a catalyst in which at least one active metal selected from the group consisting of platinum, palladium, silver, and gold is supported on brookite-type titanium oxide. This is a direct method for producing hydrogen peroxide.
<2> The method for directly producing hydrogen peroxide according to <1>, wherein the weight of the active metal is 0.01 to 10% by weight with respect to the brookite type titanium oxide.
<3> The method for directly producing hydrogen peroxide according to <1> or <2>, wherein the catalyst is hydrogen-reduced at a temperature of 400 ° C. or higher in advance.
<4> The method for directly producing hydrogen peroxide according to any one of <1> to <3>, wherein the catalyst is reduced with hydrazine.
<5> The peroxide according to any one of <1> to <4>, wherein the catalyst further supports one or more selected from the group consisting of ruthenium, rhodium, iridium, and osmium. This is a direct production method of hydrogen.
<6> The method for directly producing hydrogen peroxide according to any one of <1> to <5>, wherein the active metal is palladium and / or gold.
<7> The method for directly producing hydrogen peroxide according to <6>, wherein the active metals are palladium and gold, and the molar ratio of palladium / gold is 0.1 to 10.
<8> The method for directly producing hydrogen peroxide according to any one of <1> to <7>, wherein the brookite-type titanium oxide has a specific surface area of at least 50 m 2 / g.
<9> The method for directly producing hydrogen peroxide according to any one of <1> to <8>, wherein hydrogen peroxide is produced in the absence of an organic solvent.
<10>
The method for directly producing hydrogen peroxide according to any one of <1> to <9> above, wherein an inorganic acid selected from hydrogen halide or sulfuric acid is added to the reaction system and reacted.
<11>
The method for directly producing hydrogen peroxide according to <10>, wherein the addition amount of the inorganic acid is 0.01 to 10% by weight based on the reaction solution.
本発明の製造方法によれば、従来、触媒の担体としてよく知られたアナターゼ型あるいはルチル型の酸化チタンではなく、ブルッカイト型の酸化チタンを触媒担体として用いることにより、過酸化水素の反応速度、選択率及び収率をバランスよく向上させることができ、短時間の反応時間で高濃度の過酸化水素水溶液を得ることが出来る。また、本発明では、有機溶媒を用いる必要はないため、最終製品を得るには精製工程を必要としないという利点もある。
According to the production method of the present invention, instead of anatase type or rutile type titanium oxide, which is conventionally well known as a catalyst carrier, a brookite type titanium oxide is used as a catalyst carrier, whereby the reaction rate of hydrogen peroxide, The selectivity and yield can be improved in a well-balanced manner, and a highly concentrated aqueous hydrogen peroxide solution can be obtained in a short reaction time. In addition, in the present invention, since it is not necessary to use an organic solvent, there is an advantage that a purification step is not required to obtain a final product.
以下、本発明を詳細に説明する。
本発明における触媒担体としては、ブルッカイト型の酸化チタンであれば特に制限なく用いることができる。ブルッカイト型の酸化チタンとしては、例えば、密度４．１３ｇ／ｃｍ３、格子定数：ａ＝５．４５Å、ｂ＝９．１８Å、ｃ＝５．１５Åである結晶構造を有するものがその代表例として挙げられる。 Hereinafter, the present invention will be described in detail.
As the catalyst carrier in the present invention, any brookite type titanium oxide can be used without particular limitation. Typical examples of brookite-type titanium oxide include those having a crystal structure with a density of 4.13 g / cm 3 , lattice constants: a = 5.45 Å, b = 9.18 Å, and c = 5.15 Å. Can be mentioned.
本発明における触媒担体としては、ブルッカイト型の酸化チタンであれば特に制限なく用いることができる。ブルッカイト型の酸化チタンとしては、例えば、密度４．１３ｇ／ｃｍ３、格子定数：ａ＝５．４５Å、ｂ＝９．１８Å、ｃ＝５．１５Åである結晶構造を有するものがその代表例として挙げられる。 Hereinafter, the present invention will be described in detail.
As the catalyst carrier in the present invention, any brookite type titanium oxide can be used without particular limitation. Typical examples of brookite-type titanium oxide include those having a crystal structure with a density of 4.13 g / cm 3 , lattice constants: a = 5.45 Å, b = 9.18 Å, and c = 5.15 Å. Can be mentioned.
これらブルッカイト型の酸化チタンは、Ｘ線回折によっても同定することができる。
更に、触媒担体としては比表面積が重要であり、本発明における触媒担体であるブルッカイト型の酸化チタンは、比表面積が大きいものが望ましく、１０m2/g以上が好ましく、特に５０m2/g以上が好ましい。また、比表面積の上限は、１５０m2/g以下であることが好ましく、１００m2/g以下であることがより好ましい。 These brookite-type titanium oxides can also be identified by X-ray diffraction.
Furthermore, the specific surface area is important as the catalyst carrier, and the brookite type titanium oxide as the catalyst carrier in the present invention preferably has a large specific surface area, preferably 10 m 2 / g or more, particularly preferably 50 m 2 / g or more. preferable. Further, the upper limit of the specific surface area is preferably 150 m 2 / g or less, and more preferably 100 m 2 / g or less.
更に、触媒担体としては比表面積が重要であり、本発明における触媒担体であるブルッカイト型の酸化チタンは、比表面積が大きいものが望ましく、１０m2/g以上が好ましく、特に５０m2/g以上が好ましい。また、比表面積の上限は、１５０m2/g以下であることが好ましく、１００m2/g以下であることがより好ましい。 These brookite-type titanium oxides can also be identified by X-ray diffraction.
Furthermore, the specific surface area is important as the catalyst carrier, and the brookite type titanium oxide as the catalyst carrier in the present invention preferably has a large specific surface area, preferably 10 m 2 / g or more, particularly preferably 50 m 2 / g or more. preferable. Further, the upper limit of the specific surface area is preferably 150 m 2 / g or less, and more preferably 100 m 2 / g or less.
本発明に使用される触媒は、担体である上記ブルッカイト型の酸化チタンに、白金、パラジウム、銀及び金からなる群より選択される少なくとも１種の活性金属を担持させたものである。上記活性金属は、具体的には、白金、パラジウム、銀または金を単独もしくは混合物として、あるいは合金として用いることができる。本発明においては、本発明の効果を損なわない範囲で、更に、上記活性金属に加え、ルテニウム、オスニウム、ロジウム及びイリジウムからなる群より選択される１種以上を混合物もしくは合金としても用いることが出来る。
The catalyst used in the present invention is one in which at least one active metal selected from the group consisting of platinum, palladium, silver and gold is supported on the above brookite type titanium oxide as a carrier. Specifically, platinum, palladium, silver or gold can be used alone or as a mixture or as an alloy for the active metal. In the present invention, in addition to the above active metal, one or more selected from the group consisting of ruthenium, osnium, rhodium and iridium can be used as a mixture or alloy as long as the effects of the present invention are not impaired. .
本発明においては、上記活性金属として、パラジウムおよび／または金を使用することが好ましい。パラジウム／金のモル比は、担体であるブルッカイト型の酸化チタンに担持した場合の活性金属の分散状態によって異なるが、０．１～１０が好ましく、１～５がより好ましい。
In the present invention, it is preferable to use palladium and / or gold as the active metal. The molar ratio of palladium / gold varies depending on the dispersion state of the active metal when supported on brookite-type titanium oxide as a carrier, but is preferably 0.1 to 10, and more preferably 1 to 5.
上記活性金属を担体であるブルッカイト型の酸化チタンに担持する方法としては、含浸法またはイオン交換法を適用することが好ましい。含浸法としては、蒸発乾固法、平衡吸着法、ポアフィリング法などを適用することができる。上記活性金属の担体への担持量は、担体に対して、０．０１～１０重量％が好ましく、０．０５～５重量％がより好ましい。そして、本発明の過酸化水素の直接製造法において、触媒の使用量は、反応液に対して1～100g/lが好ましく、５～40g/lがより好ましい。
As a method for supporting the active metal on brookite type titanium oxide as a carrier, it is preferable to apply an impregnation method or an ion exchange method. As the impregnation method, an evaporation to dryness method, an equilibrium adsorption method, a pore filling method, or the like can be applied. The amount of the active metal supported on the carrier is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight based on the carrier. In the method for directly producing hydrogen peroxide according to the present invention, the amount of catalyst used is preferably 1 to 100 g / l, more preferably 5 to 40 g / l, based on the reaction solution.
更に、上記活性金属をブルッカイト型の酸化チタンに担持する方法として、活性金属の金属塩を溶解した水溶液に該酸化チタンを懸濁させた後、還元剤で還元して担持する方法も好ましく用いられる。上記還元剤としては、しゅう酸、ヒドラジンあるいはホルマリンを用いることができ、中でもヒドラジンが好ましく用いられる。そして、反応触媒として使用する際には、予め２００℃以上の温度で水素還元することが好ましく、より好ましくは３００℃、特に好ましくは４００℃以上である。
Further, as a method for supporting the active metal on brookite-type titanium oxide, a method in which the titanium oxide is suspended in an aqueous solution in which a metal salt of the active metal is dissolved and then reduced and supported by a reducing agent is also preferably used. . As the reducing agent, oxalic acid, hydrazine or formalin can be used, and hydrazine is preferably used. And when using as a reaction catalyst, it is preferable to carry out hydrogen reduction at the temperature of 200 degreeC or more beforehand, More preferably, it is 300 degreeC, Especially preferably, it is 400 degreeC or more.
尚、本発明に係る方法では、反応系に無機酸を添加して反応させることが好ましい。これにより、過酸化水素合成反応の選択率を向上させ、製造効率を確保することができる。無機酸の添加量は、反応溶液に対して０．０１～１０重量％とするのが好ましい。そして、この無機酸としては、ハロゲン化水素又は硫酸の適用が好ましく、両者のいずれか一方又は双方を添加するのが好ましい。
In the method according to the present invention, it is preferable to add an inorganic acid to the reaction system for reaction. Thereby, the selectivity of a hydrogen peroxide synthesis reaction can be improved and manufacturing efficiency can be ensured. The amount of inorganic acid added is preferably 0.01 to 10% by weight based on the reaction solution. And as this inorganic acid, application of hydrogen halide or sulfuric acid is preferable, and it is preferable to add either or both of them.
合成反応時の反応温度は、０～１００℃が好ましく、特に５～５０℃の範囲が好ましい。反応の圧力は特に制限はないが、好ましくは大気圧～１０Ｍパスカルであり、特に大気圧～２Ｍパスカルが好ましい。反応時間は、通常０．１～１００時間であり、好ましくは０．５～１０時間である。この反応は回分式でも連続式でも行うことができる。また、原料となる水素ガスと酸素ガスの流量は、爆発範囲を避け、かつ、水素に対して酸素が過剰となるような割合が好ましい。
The reaction temperature during the synthesis reaction is preferably from 0 to 100 ° C., particularly preferably from 5 to 50 ° C. The pressure of the reaction is not particularly limited, but is preferably atmospheric pressure to 10M Pascal, and particularly preferably atmospheric pressure to 2M Pascal. The reaction time is usually 0.1 to 100 hours, preferably 0.5 to 10 hours. This reaction can be carried out either batchwise or continuously. Further, the flow rates of the hydrogen gas and oxygen gas as raw materials are preferably such that the explosion range is avoided and oxygen is excessive with respect to hydrogen.
本発明においては、水素の反応率は、３０％以上が好ましく、４０％以上がより好ましい。また、本発明においては、過酸化水素の選択率は、４０％以上が好ましく、６０％以上がより好ましい。更に、本発明においては、過酸化水素の収率は、２５％以上が好ましい。
In the present invention, the hydrogen reaction rate is preferably 30% or more, and more preferably 40% or more. In the present invention, the selectivity for hydrogen peroxide is preferably 40% or more, and more preferably 60% or more. Furthermore, in the present invention, the yield of hydrogen peroxide is preferably 25% or more.
以下、実施例および比較例に基づいて、本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。
Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.
（実施例１）
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）10g、HAuCl40.05gおよびPdCl20.12gを水300mlに懸濁し、60℃まで加熱した。NaOH(2.5×10－4mol/ml)をpH10になるまで加えた後、3%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、85℃乾燥機で一晩乾燥させた。この乾燥試料を0.5～1.8mmに整粒し、450℃、40ml/minのH2気流中で4時間還元処理を行うことにより、黒色の粒状触媒を得た。得られた触媒のX線回折を調べた。その結果を図１に示す。
攪拌装置およびガス吹き込み管を備えたテフロンで内張りをした２３０ｍｌのオートクレイブに、上記で製造したＡｕ/Ｐｄ担持のブルッカイト型チタニア触媒１．５ｇ、ＮａＣｌ０．３６８ｇ、及び硫酸２．８ｇを蒸留水で希釈し、全量が７５ｍｌとなるように仕込んだ。オートクレイブを１０℃に調整しながら、ガスを５０ｍｌ/ｍｉｎ（水素：２．５％、酸素：１９．５％、窒素：３０％、アルゴン：４８％）でオートクレイブに吹き込みながら圧力を０．１Ｍパスカルに調整し、回転数８００ｒｐｍで攪拌しながら２時間反応させた。
（１）過酸化水素の生成速度は、以下のように求めた。
過酸化水素生成速度＝（生成した過酸化水素モル濃度）÷（反応時間）
なお、生成した過酸化水素のモル濃度は、硫酸チタニルを過酸化水素の発色剤として使用し、紫外可視分光光度計（商品名：V-550、日本分光製）を用いて測定した。
（２）水素の反応率は、以下のように求めた。
水素の反応率＝（消費された水素量）÷（吹き込んだ水素の全量）
なお、消費された水素量は、ガスクロマトグラフィー（商品名：GC-8A、島津製作所製）を用いて測定した。
（３）過酸化水素の選択率は次式によって計算した。
過酸化水素の選択率（％）＝［（反応により生成した過酸化水素のモル量）÷（消費された水素量から算出した過酸化水素の理論生成モル量）］×１００
なお、生成した過酸化水素のモル量は、硫酸チタニルを過酸化水素の発色剤として使用し、紫外可視分光光度計（商品名：V-550、日本分光製）を用いて測定した。
（４）過酸化水素の収率は、以下のように求めた。
過酸化水素の収率＝（水素の反応率）×（過酸化水素の選択率）
これらの結果を表１に示す。 Example 1
Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g, HAuCl 4 0.05 g and PdCl 2 0.12 g were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 × 10 −4 mol / ml) was added untilpH 10 and then a 3% aqueous hydrazine solution was added dropwise. When the color change ceased, the end of the reduction was judged, and the water was removed by heating until it became semi-liquid while stirring with a magnetic stirrer. Further, after removing the magnetic stirrer, the magnetic stirrer was dried overnight in a 85 ° C. dryer. The dried sample was sized to 0.5 to 1.8 mm and subjected to reduction treatment for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst. The obtained catalyst was examined for X-ray diffraction. The result is shown in FIG.
To a 230 ml autoclave lined with Teflon equipped with a stirrer and a gas blowing tube, 1.5 g of the Au / Pd-supported brookite-type titania catalyst, 0.368 g of NaCl, and 2.8 g of sulfuric acid were added with distilled water. Diluted and charged to a total volume of 75 ml. While adjusting the autoclave to 10 ° C., the gas was blown into the autoclave at 50 ml / min (hydrogen: 2.5%, oxygen: 19.5%, nitrogen: 30%, argon: 48%), and the pressure was adjusted to 0. The mixture was adjusted to 1 M Pascal and reacted for 2 hours while stirring at a rotation speed of 800 rpm.
(1) The production rate of hydrogen peroxide was determined as follows.
Hydrogen peroxide production rate = (Molar concentration of hydrogen peroxide produced) ÷ (Reaction time)
The molar concentration of the generated hydrogen peroxide was measured using an ultraviolet-visible spectrophotometer (trade name: V-550, manufactured by JASCO Corporation) using titanyl sulfate as a coloring agent for hydrogen peroxide.
(2) The reaction rate of hydrogen was determined as follows.
Hydrogen reaction rate = (amount of hydrogen consumed) ÷ (total amount of hydrogen injected)
The amount of hydrogen consumed was measured using gas chromatography (trade name: GC-8A, manufactured by Shimadzu Corporation).
(3) The selectivity for hydrogen peroxide was calculated by the following equation.
Hydrogen peroxide selectivity (%) = [(molar amount of hydrogen peroxide produced by reaction) ÷ (theoretical molar amount of hydrogen peroxide calculated from the amount of hydrogen consumed)] × 100
The molar amount of hydrogen peroxide produced was measured using an ultraviolet-visible spectrophotometer (trade name: V-550, manufactured by JASCO Corporation) using titanyl sulfate as a color former for hydrogen peroxide.
(4) The yield of hydrogen peroxide was determined as follows.
Hydrogen peroxide yield = (hydrogen reaction rate) x (hydrogen peroxide selectivity)
These results are shown in Table 1.
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）10g、HAuCl40.05gおよびPdCl20.12gを水300mlに懸濁し、60℃まで加熱した。NaOH(2.5×10－4mol/ml)をpH10になるまで加えた後、3%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、85℃乾燥機で一晩乾燥させた。この乾燥試料を0.5～1.8mmに整粒し、450℃、40ml/minのH2気流中で4時間還元処理を行うことにより、黒色の粒状触媒を得た。得られた触媒のX線回折を調べた。その結果を図１に示す。
攪拌装置およびガス吹き込み管を備えたテフロンで内張りをした２３０ｍｌのオートクレイブに、上記で製造したＡｕ/Ｐｄ担持のブルッカイト型チタニア触媒１．５ｇ、ＮａＣｌ０．３６８ｇ、及び硫酸２．８ｇを蒸留水で希釈し、全量が７５ｍｌとなるように仕込んだ。オートクレイブを１０℃に調整しながら、ガスを５０ｍｌ/ｍｉｎ（水素：２．５％、酸素：１９．５％、窒素：３０％、アルゴン：４８％）でオートクレイブに吹き込みながら圧力を０．１Ｍパスカルに調整し、回転数８００ｒｐｍで攪拌しながら２時間反応させた。
（１）過酸化水素の生成速度は、以下のように求めた。
過酸化水素生成速度＝（生成した過酸化水素モル濃度）÷（反応時間）
なお、生成した過酸化水素のモル濃度は、硫酸チタニルを過酸化水素の発色剤として使用し、紫外可視分光光度計（商品名：V-550、日本分光製）を用いて測定した。
（２）水素の反応率は、以下のように求めた。
水素の反応率＝（消費された水素量）÷（吹き込んだ水素の全量）
なお、消費された水素量は、ガスクロマトグラフィー（商品名：GC-8A、島津製作所製）を用いて測定した。
（３）過酸化水素の選択率は次式によって計算した。
過酸化水素の選択率（％）＝［（反応により生成した過酸化水素のモル量）÷（消費された水素量から算出した過酸化水素の理論生成モル量）］×１００
なお、生成した過酸化水素のモル量は、硫酸チタニルを過酸化水素の発色剤として使用し、紫外可視分光光度計（商品名：V-550、日本分光製）を用いて測定した。
（４）過酸化水素の収率は、以下のように求めた。
過酸化水素の収率＝（水素の反応率）×（過酸化水素の選択率）
これらの結果を表１に示す。 Example 1
Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g, HAuCl 4 0.05 g and PdCl 2 0.12 g were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 × 10 −4 mol / ml) was added until
To a 230 ml autoclave lined with Teflon equipped with a stirrer and a gas blowing tube, 1.5 g of the Au / Pd-supported brookite-type titania catalyst, 0.368 g of NaCl, and 2.8 g of sulfuric acid were added with distilled water. Diluted and charged to a total volume of 75 ml. While adjusting the autoclave to 10 ° C., the gas was blown into the autoclave at 50 ml / min (hydrogen: 2.5%, oxygen: 19.5%, nitrogen: 30%, argon: 48%), and the pressure was adjusted to 0. The mixture was adjusted to 1 M Pascal and reacted for 2 hours while stirring at a rotation speed of 800 rpm.
(1) The production rate of hydrogen peroxide was determined as follows.
Hydrogen peroxide production rate = (Molar concentration of hydrogen peroxide produced) ÷ (Reaction time)
The molar concentration of the generated hydrogen peroxide was measured using an ultraviolet-visible spectrophotometer (trade name: V-550, manufactured by JASCO Corporation) using titanyl sulfate as a coloring agent for hydrogen peroxide.
(2) The reaction rate of hydrogen was determined as follows.
Hydrogen reaction rate = (amount of hydrogen consumed) ÷ (total amount of hydrogen injected)
The amount of hydrogen consumed was measured using gas chromatography (trade name: GC-8A, manufactured by Shimadzu Corporation).
(3) The selectivity for hydrogen peroxide was calculated by the following equation.
Hydrogen peroxide selectivity (%) = [(molar amount of hydrogen peroxide produced by reaction) ÷ (theoretical molar amount of hydrogen peroxide calculated from the amount of hydrogen consumed)] × 100
The molar amount of hydrogen peroxide produced was measured using an ultraviolet-visible spectrophotometer (trade name: V-550, manufactured by JASCO Corporation) using titanyl sulfate as a color former for hydrogen peroxide.
(4) The yield of hydrogen peroxide was determined as follows.
Hydrogen peroxide yield = (hydrogen reaction rate) x (hydrogen peroxide selectivity)
These results are shown in Table 1.
（実施例２）
(蒸発乾固法)
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）１０ｇ、ＨＡｕＣｌ４０．０５ｇおよびＰｄＣｌ２０．１２ｇを水１００ｍｌに懸濁した。マグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、６０℃にて一晩乾燥した。この乾燥試料を粉砕後、０．５～１．１８ｍｍに整粒し、４５０℃、４０ｍｌ／ｍｉｎのＨ２気流中で４時間還元処理を行うことにより、黒色の粒状触媒を得た。得られた触媒のＸ線回折を調べた。その結果を図２に示す。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Example 2)
(Evaporation to dryness method)
Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g, HAuCl 4 0.05 g and PdCl 2 0.12 g were suspended in 100 ml of water. While stirring with a magnetic stirrer, the water was removed by heating until it became semi-liquid. Furthermore, after removing the magnetic stirrer, it was dried at 60 ° C. overnight. The dried sample was pulverized, sized to 0.5 to 1.18 mm, and reduced for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst. The obtained catalyst was examined for X-ray diffraction. The result is shown in FIG.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
(蒸発乾固法)
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）１０ｇ、ＨＡｕＣｌ４０．０５ｇおよびＰｄＣｌ２０．１２ｇを水１００ｍｌに懸濁した。マグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、６０℃にて一晩乾燥した。この乾燥試料を粉砕後、０．５～１．１８ｍｍに整粒し、４５０℃、４０ｍｌ／ｍｉｎのＨ２気流中で４時間還元処理を行うことにより、黒色の粒状触媒を得た。得られた触媒のＸ線回折を調べた。その結果を図２に示す。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Example 2)
(Evaporation to dryness method)
Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g, HAuCl 4 0.05 g and PdCl 2 0.12 g were suspended in 100 ml of water. While stirring with a magnetic stirrer, the water was removed by heating until it became semi-liquid. Furthermore, after removing the magnetic stirrer, it was dried at 60 ° C. overnight. The dried sample was pulverized, sized to 0.5 to 1.18 mm, and reduced for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst. The obtained catalyst was examined for X-ray diffraction. The result is shown in FIG.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
（実施例３）
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）１０g、ＨＡｕＣｌ４０．０８６gおよびＰｄＣｌ２０．２０３gを水３００mlに懸濁し、６０℃まで加熱した。NaOH(2.5×10－4mol/ml)をｐＨ１０になるまで加えた後、３%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、８５℃乾燥機で一晩乾燥させた。この乾燥試料を０．５～１．８mmに整粒し、粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Example 3)
Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g, HAuCl 4 0.086 g and PdCl 2 0.203 g were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 × 10 −4 mol / ml) was added untilpH 10 and 3% aqueous hydrazine solution was added dropwise. When the color change ceased, the end of the reduction was judged, and the water was removed by heating until it became semi-liquid while stirring with a magnetic stirrer. Further, after removing the magnetic stirrer, the magnetic stirrer was dried overnight in an 85 ° C. dryer. The dried sample was sized to 0.5 to 1.8 mm to obtain a granular catalyst.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）１０g、ＨＡｕＣｌ４０．０８６gおよびＰｄＣｌ２０．２０３gを水３００mlに懸濁し、６０℃まで加熱した。NaOH(2.5×10－4mol/ml)をｐＨ１０になるまで加えた後、３%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、８５℃乾燥機で一晩乾燥させた。この乾燥試料を０．５～１．８mmに整粒し、粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Example 3)
Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g, HAuCl 4 0.086 g and PdCl 2 0.203 g were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 × 10 −4 mol / ml) was added until
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
（実施例４）
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）１０g、ＰｄＣｌ２０．２０３g を水３００mlに懸濁し、６０℃まで加熱した。NaOH(2.5×10－4mol/ml)をｐＨ１０になるまで加えた後、３%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、８５℃乾燥機で一晩乾燥させた。この乾燥試料を０．５～１．８mmに整粒し、粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 Example 4
Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g and PdCl 2 0.203 g were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 × 10 −4 mol / ml) was added untilpH 10 and 3% aqueous hydrazine solution was added dropwise. When the color change ceased, the end of the reduction was judged, and the water was removed by heating until it became semi-liquid while stirring with a magnetic stirrer. Further, after removing the magnetic stirrer, the magnetic stirrer was dried overnight in an 85 ° C. dryer. The dried sample was sized to 0.5 to 1.8 mm to obtain a granular catalyst.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）１０g、ＰｄＣｌ２０．２０３g を水３００mlに懸濁し、６０℃まで加熱した。NaOH(2.5×10－4mol/ml)をｐＨ１０になるまで加えた後、３%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、８５℃乾燥機で一晩乾燥させた。この乾燥試料を０．５～１．８mmに整粒し、粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 Example 4
Showa Denko high surface area brookite type titania (specific surface area 74 m 2 / g) 10 g and PdCl 2 0.203 g were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 × 10 −4 mol / ml) was added until
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
（実施例５）
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）１０g、ＰｄＣｌ２０．２０３g および Pt(NH3)4Cl2・H2O ０．２２ｇを水３００mlに懸濁し、６０℃まで加熱した。NaOH(2.5×10－4mol/ml)をｐＨ１０になるまで加えた後、３%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、８５℃乾燥機で一晩乾燥させた。この乾燥試料を０．５～１．８mmに整粒し、粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Example 5)
Showa Denko high surface area brookite type titania (specific surface area 74m 2 / g) 10g, PdCl 2 0.203g and Pt (NH 3 ) 4 Cl 2 · H 2 O 0.22g suspended in 300ml water up to 60 ° C Heated. NaOH (2.5 × 10 −4 mol / ml) was added untilpH 10 and 3% aqueous hydrazine solution was added dropwise. When the color change ceased, the end of the reduction was judged, and the water was removed by heating until it became semi-liquid while stirring with a magnetic stirrer. Further, after removing the magnetic stirrer, the magnetic stirrer was dried overnight in an 85 ° C. dryer. The dried sample was sized to 0.5 to 1.8 mm to obtain a granular catalyst.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
昭和電工製高表面積ブルッカイト型チタニア（比表面積が７４m2／g）１０g、ＰｄＣｌ２０．２０３g および Pt(NH3)4Cl2・H2O ０．２２ｇを水３００mlに懸濁し、６０℃まで加熱した。NaOH(2.5×10－4mol/ml)をｐＨ１０になるまで加えた後、３%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、８５℃乾燥機で一晩乾燥させた。この乾燥試料を０．５～１．８mmに整粒し、粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Example 5)
Showa Denko high surface area brookite type titania (specific surface area 74m 2 / g) 10g, PdCl 2 0.203g and Pt (NH 3 ) 4 Cl 2 · H 2 O 0.22g suspended in 300ml water up to 60 ° C Heated. NaOH (2.5 × 10 −4 mol / ml) was added until
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
（比較例１）
事前に500℃で2時間空気焼成した堺化学製ルチル型チタニア（STR-100N、表面積38m2/g）１０ｇ、ＨＡｕＣｌ4０．０５ｇおよびＰｄＣｌ２０．１２ｇを水１００ｍｌに懸濁した。マグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、６０℃にて一晩乾燥した。この乾燥試料を粉砕後、０．５～１．１８ｍｍに整粒し、４５０℃、４０ｍｌ／ｍｉｎのＨ２気流中で４時間還元処理を行うことにより、黒色の粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Comparative Example 1)
Pre and 2 hours air calcined at 500 ° C. Sakai Kagaku rutile titania (STR-100N, surface area 38m 2 / g) 10g, the HAuCl 4 0.05 g and PdCl 2 0.12 g was suspended in water 100 ml. While stirring with a magnetic stirrer, the water was removed by heating until it became semi-liquid. Furthermore, after removing the magnetic stirrer, it was dried at 60 ° C. overnight. The dried sample was pulverized, sized to 0.5 to 1.18 mm, and reduced for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
事前に500℃で2時間空気焼成した堺化学製ルチル型チタニア（STR-100N、表面積38m2/g）１０ｇ、ＨＡｕＣｌ4０．０５ｇおよびＰｄＣｌ２０．１２ｇを水１００ｍｌに懸濁した。マグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、６０℃にて一晩乾燥した。この乾燥試料を粉砕後、０．５～１．１８ｍｍに整粒し、４５０℃、４０ｍｌ／ｍｉｎのＨ２気流中で４時間還元処理を行うことにより、黒色の粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Comparative Example 1)
Pre and 2 hours air calcined at 500 ° C. Sakai Kagaku rutile titania (STR-100N, surface area 38m 2 / g) 10g, the HAuCl 4 0.05 g and PdCl 2 0.12 g was suspended in water 100 ml. While stirring with a magnetic stirrer, the water was removed by heating until it became semi-liquid. Furthermore, after removing the magnetic stirrer, it was dried at 60 ° C. overnight. The dried sample was pulverized, sized to 0.5 to 1.18 mm, and reduced for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
（比較例２）
堺化学製ルチル型チタニア（STR-100N、表面積38m2/g）１０ｇ、ＨＡｕＣｌ4０．０５ｇおよびＰｄＣｌ２０．１２ｇを水300mlに懸濁し、60℃まで加熱した。NaOH(2.5×10－4mol/ml)をpH10になるまで加えた後、3%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、85℃乾燥機で一晩乾燥させた。この乾燥試料を0.5～1.8mmに整粒し、450℃、40ml/minのH2気流中で4時間還元処理を行うことにより、黒色の粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Comparative Example 2)
10 g of rutile type titania (STR-100N, surface area 38 m 2 / g) manufactured by Sakai Chemical, 0.05 g of HAuCl 4 and 0.12 g of PdCl 2 were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 × 10 −4 mol / ml) was added untilpH 10 and then a 3% aqueous hydrazine solution was added dropwise. When the color change ceased, the end of the reduction was judged, and the water was removed by heating until it became semi-liquid while stirring with a magnetic stirrer. Further, after removing the magnetic stirrer, the magnetic stirrer was dried overnight in a 85 ° C. dryer. The dried sample was sized to 0.5 to 1.8 mm and subjected to reduction treatment for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
堺化学製ルチル型チタニア（STR-100N、表面積38m2/g）１０ｇ、ＨＡｕＣｌ4０．０５ｇおよびＰｄＣｌ２０．１２ｇを水300mlに懸濁し、60℃まで加熱した。NaOH(2.5×10－4mol/ml)をpH10になるまで加えた後、3%ヒドラジン水溶液を滴下した。色の変化がなくなったところで還元終了を判断し、引き続きマグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、85℃乾燥機で一晩乾燥させた。この乾燥試料を0.5～1.8mmに整粒し、450℃、40ml/minのH2気流中で4時間還元処理を行うことにより、黒色の粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Comparative Example 2)
10 g of rutile type titania (STR-100N, surface area 38 m 2 / g) manufactured by Sakai Chemical, 0.05 g of HAuCl 4 and 0.12 g of PdCl 2 were suspended in 300 ml of water and heated to 60 ° C. NaOH (2.5 × 10 −4 mol / ml) was added until
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
（比較例３）
キシダ化学製アナターゼ型チタニア（020-78675；表面積5.8m2/g）１０ｇ、ＨＡｕＣｌ4０．０５ｇおよびＰｄＣｌ２０．１２ｇを水１００ｍｌに懸濁した。マグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、６０℃にて一晩乾燥した。この乾燥試料を粉砕後、０．５～１．１８ｍｍに整粒し、４５０℃、４０ｍｌ／ｍｉｎのＨ２気流中で４時間還元処理を行うことにより、黒色の粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Comparative Example 3)
10 g of anatase titania (020-78675; surface area 5.8 m 2 / g) manufactured by Kishida Chemical Co., Ltd., 0.05 g of HAuCl 4 and 0.12 g of PdCl 2 were suspended in 100 ml of water. While stirring with a magnetic stirrer, the water was removed by heating until it became semi-liquid. Furthermore, after removing the magnetic stirrer, it was dried at 60 ° C. overnight. The dried sample was pulverized, sized to 0.5 to 1.18 mm, and reduced for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
キシダ化学製アナターゼ型チタニア（020-78675；表面積5.8m2/g）１０ｇ、ＨＡｕＣｌ4０．０５ｇおよびＰｄＣｌ２０．１２ｇを水１００ｍｌに懸濁した。マグネチックスターラーで攪拌しながら、加熱して半液体状になるまで水分を除去した。さらに、マグネチックスターラーを除去後、６０℃にて一晩乾燥した。この乾燥試料を粉砕後、０．５～１．１８ｍｍに整粒し、４５０℃、４０ｍｌ／ｍｉｎのＨ２気流中で４時間還元処理を行うことにより、黒色の粒状触媒を得た。
上記で得られた触媒を使用した以外は、実施例１と同様に過酸化水素を製造した。得られた結果を表１に示す。 (Comparative Example 3)
10 g of anatase titania (020-78675; surface area 5.8 m 2 / g) manufactured by Kishida Chemical Co., Ltd., 0.05 g of HAuCl 4 and 0.12 g of PdCl 2 were suspended in 100 ml of water. While stirring with a magnetic stirrer, the water was removed by heating until it became semi-liquid. Furthermore, after removing the magnetic stirrer, it was dried at 60 ° C. overnight. The dried sample was pulverized, sized to 0.5 to 1.18 mm, and reduced for 4 hours in a H 2 stream at 450 ° C. and 40 ml / min to obtain a black granular catalyst.
Hydrogen peroxide was produced in the same manner as in Example 1 except that the catalyst obtained above was used. The obtained results are shown in Table 1.
表１に示した結果から明らかな通り、実施例１から５で使用したブルッカイト型チタニアに特定の活性金属を担持させた触媒を用いた本発明の過酸化水素の製造方法によれば、ルチル型チタニア及びアナターゼ型チタニアに金属を担持させた触媒を用いた過酸化水素の製造方法に比べて、過酸化水素の生成速度、選択率及び収率がバランスよく優れ、特に選択率が高く工業的な価値が認められた。特にガス循環型の反応系を考えた場合は選択率が高い事は非常に経済的に有利である。
As is apparent from the results shown in Table 1, according to the method for producing hydrogen peroxide of the present invention using the catalyst in which a specific active metal is supported on the brookite type titania used in Examples 1 to 5, the rutile type is used. Compared to the production method of hydrogen peroxide using a catalyst in which a metal is supported on titania and anatase titania, the production rate, selectivity and yield of hydrogen peroxide are well balanced, and the selectivity is particularly high and industrial. Value was recognized. Particularly when considering a gas circulation type reaction system, a high selectivity is very economically advantageous.
Claims (11)
- ブルッカイト型の酸化チタンに、白金、パラジウム、銀及び金からなる群より選択される少なくとも１種の活性金属を担持させた触媒の存在下で、水素と酸素とを反応させる工程を有する過酸化水素の直接製造法。 Hydrogen peroxide having a step of reacting hydrogen and oxygen in the presence of a catalyst in which at least one active metal selected from the group consisting of platinum, palladium, silver and gold is supported on brookite-type titanium oxide Direct manufacturing method.
- 前記活性金属の重量が、前記ブルッカイト型の酸化チタンに対して０．０１～１０重量％である、請求項１に記載の過酸化水素の直接製造法。 The method for directly producing hydrogen peroxide according to claim 1, wherein the weight of the active metal is 0.01 to 10% by weight with respect to the brookite-type titanium oxide.
- 前記触媒が、予め４００℃以上の温度で水素還元されたものである、請求項１または２に記載の過酸化水素の直接製造法。 The direct production method of hydrogen peroxide according to claim 1 or 2, wherein the catalyst is previously hydrogen-reduced at a temperature of 400 ° C or higher.
- 前記触媒が、ヒドラジンによって還元されたものである、請求項１から３のいずれかに記載の過酸化水素の直接製造法。 The method for directly producing hydrogen peroxide according to any one of claims 1 to 3, wherein the catalyst is reduced with hydrazine.
- 前記触媒が、更に、ルテニウム、ロジウム、イリジウム及びオスミウムからなる群より選択される１種以上を担持させたものである、請求項１から４のいずれかに記載の過酸化水素の直接製造法。 The method for directly producing hydrogen peroxide according to any one of claims 1 to 4, wherein the catalyst further supports one or more selected from the group consisting of ruthenium, rhodium, iridium and osmium.
- 前記活性金属が、パラジウムおよび／または金である、請求項１から５のいずれかに記載の過酸化水素の直接製造法。 The method for directly producing hydrogen peroxide according to any one of claims 1 to 5, wherein the active metal is palladium and / or gold.
- 前記活性金属が、パラジウムおよび金であり、パラジウム／金のモル比が０．１～１０である、請求項６に記載の過酸化水素の直接製造法。 The method for directly producing hydrogen peroxide according to claim 6, wherein the active metals are palladium and gold, and the molar ratio of palladium / gold is 0.1 to 10.
- 前記ブルッカイト型の酸化チタンが、少なくとも５０ｍ２／ｇの比表面積を有する、請求項１から７のいずれかに記載の過酸化水素の直接製造法。 The method for directly producing hydrogen peroxide according to any one of claims 1 to 7, wherein the brookite type titanium oxide has a specific surface area of at least 50 m 2 / g.
- 有機溶媒の不存在下で過酸化水素を製造する、請求項１から８のいずれかに記載の過酸化水素の直接製造法。 The method for directly producing hydrogen peroxide according to any one of claims 1 to 8, wherein hydrogen peroxide is produced in the absence of an organic solvent.
- 反応系にハロゲン化水素又は硫酸から選択される無機酸を添加して反応させる、請求項１から９のいずれかに記載の過酸化水素の直接製造法。 The method for directly producing hydrogen peroxide according to any one of claims 1 to 9, wherein an inorganic acid selected from hydrogen halide or sulfuric acid is added to the reaction system for reaction.
- 前記無機酸の添加量が、反応溶液に対して０．０１～１０重量％である、請求項１０に記載の過酸化水素の直接製造法。 The method for directly producing hydrogen peroxide according to claim 10, wherein the added amount of the inorganic acid is 0.01 to 10% by weight with respect to the reaction solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011074746A JP2014114167A (en) | 2011-03-30 | 2011-03-30 | Method for direct production of hydrogen peroxide using brookite type titanium oxide |
| JP2011-074746 | 2011-03-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012133149A1 true WO2012133149A1 (en) | 2012-10-04 |
Family
ID=46930873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2012/057454 WO2012133149A1 (en) | 2011-03-30 | 2012-03-23 | Method for direct production of hydrogen peroxide using brookite type titanium oxide |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2014114167A (en) |
| TW (1) | TW201302604A (en) |
| WO (1) | WO2012133149A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014010372A1 (en) * | 2012-07-10 | 2014-01-16 | 三菱瓦斯化学株式会社 | Method for producing hydrogen peroxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517276B (en) * | 2019-02-02 | 2021-12-24 | 国家纳米科学中心 | Method for preparing hydrogen and hydrogen peroxide by photocatalytic water decomposition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5518646B2 (en) * | 1975-12-10 | 1980-05-20 | ||
| JP2004518604A (en) * | 2000-12-21 | 2004-06-24 | アルコ ケミカル テクノロジィ， エル．ピー． | Method for producing hydrogen peroxide |
| JP2009500171A (en) * | 2005-07-11 | 2009-01-08 | ユニバーシティ・カレッジ・カーディフ・コンサルタンツ・リミテッド | Improvement of catalyst |
| JP2010143810A (en) * | 2008-12-22 | 2010-07-01 | Kyushu Univ | Method for directly producing hydrogen peroxide by using ionic liquid |
-
2011
- 2011-03-30 JP JP2011074746A patent/JP2014114167A/en not_active Withdrawn
-
2012
- 2012-03-21 TW TW101109640A patent/TW201302604A/en unknown
- 2012-03-23 WO PCT/JP2012/057454 patent/WO2012133149A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5518646B2 (en) * | 1975-12-10 | 1980-05-20 | ||
| JP2004518604A (en) * | 2000-12-21 | 2004-06-24 | アルコ ケミカル テクノロジィ， エル．ピー． | Method for producing hydrogen peroxide |
| JP2009500171A (en) * | 2005-07-11 | 2009-01-08 | ユニバーシティ・カレッジ・カーディフ・コンサルタンツ・リミテッド | Improvement of catalyst |
| JP2010143810A (en) * | 2008-12-22 | 2010-07-01 | Kyushu Univ | Method for directly producing hydrogen peroxide by using ionic liquid |
Non-Patent Citations (1)
| Title |
|---|
| KOHEI MODA ET AL.: "Ti02 Tanji Pd-Au Shokubai ni yoru H2 karano Chokusetsu H202 Gosei", DAI 105 KAI SHOKUBAI TORONKAI TORONKAI A YOKOSHU, 24 March 2010 (2010-03-24), pages 123, XP008176216 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014010372A1 (en) * | 2012-07-10 | 2014-01-16 | 三菱瓦斯化学株式会社 | Method for producing hydrogen peroxide |
| JP2014015353A (en) * | 2012-07-10 | 2014-01-30 | Mitsubishi Gas Chemical Co Inc | Method for producing hydrogen peroxide |
| US9919923B2 (en) | 2012-07-10 | 2018-03-20 | Mitsubishi Gas Chemical Company, Inc. | Method for producing hydrogen peroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201302604A (en) | 2013-01-16 |
| JP2014114167A (en) | 2014-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5073133B2 (en) | Catalyst and method for direct synthesis of hydrogen peroxide | |
| TWI229052B (en) | Process for the continuous production of hydrogen peroxide | |
| KR100284671B1 (en) | Method of producing hydrogen peroxide | |
| JP5588107B2 (en) | Improvement of catalyst | |
| KR20180024478A (en) | Nano-catalyst for preparing hydrogen peroxide having mesoporous shell and method for preparing hydrogen peroxide using the same | |
| WO2013068340A1 (en) | A catalyst for direct synthesis of hydrogen peroxide | |
| TWI238857B (en) | Direct synthesis of hydrogen peroxide in a multicomponent solvent system | |
| WO2012133149A1 (en) | Method for direct production of hydrogen peroxide using brookite type titanium oxide | |
| JP5048643B2 (en) | Direct production method of hydrogen peroxide using ionic liquid | |
| JP2008212872A (en) | Catalyst, its production method and production method of hydrogen peroxide | |
| KR101825907B1 (en) | Catalyst for preparing hydrogen peroxide having core-shell structure and method for preparing hydrogen peroxide using the same | |
| Mehri et al. | In Situ Generated H2O2 over Supported Pd–Au Clusters in Hybrid Titania Nanocrystallites | |
| US9610573B2 (en) | Process to obtain hydrogen peroxide, and catalyst supports for the same process | |
| WO2018016359A1 (en) | Noble metal catalyst for manufacturing hydrogen peroxide, and method for manufacturing hydrogen peroxide | |
| CN114618486B (en) | Platinum-palladium-silver compound catalyst and preparation method and application thereof | |
| JP2013146720A (en) | Method for producing supported ruthenium oxide, and method for production of chlorine | |
| WO2016050859A2 (en) | Method for preparing a catalyst support and a catalyst | |
| RU2526460C1 (en) | Method of preparing catalyst and method of obtaining hydrogen peroxide | |
| EP3107652A1 (en) | Process to obtain hydrogen peroxide, and catalyst and catalysts supports for said process | |
| Tawkaew et al. | Preparation and photocatalytic activity of iron oxide-loaded potassium titanate layered compounds | |
| JP2019181332A (en) | Catalyst for decomposing hydrogen iodide | |
| EP3160901A1 (en) | A catalyst for direct synthesis of hydrogen peroxide, its preparation and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12763009 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 12763009 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: JP |