CN109310998A - Precious metal catalyst for hydrogen peroxide production and method for producing hydrogen peroxide - Google Patents
Precious metal catalyst for hydrogen peroxide production and method for producing hydrogen peroxide Download PDFInfo
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- CN109310998A CN109310998A CN201780036190.4A CN201780036190A CN109310998A CN 109310998 A CN109310998 A CN 109310998A CN 201780036190 A CN201780036190 A CN 201780036190A CN 109310998 A CN109310998 A CN 109310998A
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- Prior art keywords
- oxygen
- metal catalyst
- hydrogen
- noble metal
- hydrogen peroxide
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000010970 precious metal Substances 0.000 title description 23
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 97
- 239000001257 hydrogen Substances 0.000 claims abstract description 95
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 95
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 77
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 73
- 239000001301 oxygen Substances 0.000 claims abstract description 73
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000007789 gas Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 62
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000012429 reaction media Substances 0.000 claims abstract description 42
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 30
- 239000010931 gold Substances 0.000 claims abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052737 gold Inorganic materials 0.000 claims abstract description 13
- 238000004969 ion scattering spectroscopy Methods 0.000 claims description 39
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052794 bromium Inorganic materials 0.000 claims description 22
- 239000004615 ingredient Substances 0.000 claims description 19
- 238000004458 analytical method Methods 0.000 claims description 14
- 238000001514 detection method Methods 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 13
- 239000003863 metallic catalyst Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 54
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 239000012018 catalyst precursor Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 150000002431 hydrogen Chemical class 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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 5
- 150000004056 anthraquinones Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- -1 phosphonate ester Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 229940123457 Free radical scavenger Drugs 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229940062054 oxygen 30 % Drugs 0.000 description 4
- 229940063729 oxygen 80 % Drugs 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 3
- 229940006460 bromide ion Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005443 coulometric titration Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229940103062 oxygen 25 % Drugs 0.000 description 2
- 229940062042 oxygen 50 % Drugs 0.000 description 2
- 229940103067 oxygen 60 % Drugs 0.000 description 2
- 229940062173 oxygen 70 % Drugs 0.000 description 2
- QVGXLLKOCUKJST-NJFSPNSNSA-N oxygen-18 atom Chemical compound [18O] QVGXLLKOCUKJST-NJFSPNSNSA-N 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 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
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940038031 nitrogen 10 % Drugs 0.000 description 1
- 229940063896 nitrogen 60 % Drugs 0.000 description 1
- 229940062100 nitrogen 72 % Drugs 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
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 the noble metal catalyst and peroxidating method for preparing hydrogen of a kind of hydrogen peroxide that can manufacture high concentration.The noble metal catalyst is to obtain noble metal catalyst used in the method for hydrogen peroxide reacting hydrogen and oxygen directly, includes palladium, gold, oxygen atom and bromine atom, and above-mentioned oxygen atom and bromine atom are present in the outmost surface of noble metal catalyst；And, the peroxidating method for preparing hydrogen includes: that the step of including the gas of hydrogen and oxygen is imported in reaction medium, with the step of in reaction medium, making the hydrogen imported and oxygen contact under the pressure of 0.1MPa or more with above-mentioned noble metal catalyst and obtain hydrogen peroxide.
Description
Technical field
The present invention relates to react hydrogen and oxygen directly and obtain noble metal catalyst used in the method for hydrogen peroxide,
And the peroxidating method for preparing hydrogen using the noble metal catalyst.
Background technique
Hydrogen peroxide has oxidizing force and possesses the bleaching of strength, bactericidal effect, therefore as paper, slurry, fiber etc.
Bleaching agent, fungicide utilize, in addition, and in the oxidation reaction based on epoxidation and hydroxylating it is widely used important
Industrial product.
In addition, hydrogen peroxide closes in semiconductor industry for the cleaning on the surfaces such as semiconductor substrate, copper, tin and other copper
Grinding and the etching of electronic circuit of the chemistry of gold surface etc..Moreover, the decomposition product of hydrogen peroxide be water and oxygen, because
This, is in important position from the viewpoint of Green Chemistry, as being also concerned instead of material for chlorine system bleaching agent.
Currently, the autofrettage as hydrogen peroxide, it is known to anthraquinone, electrolysis method, using method of isopropanol oxidation etc.,
Industrially mainly using anthraquinone.However, it is anthraquinone be include anthraquinone plus hydrogen, the oxidation of air, the peroxidating that is generated by water
Multistage method as the extraction of hydrogen, further purification, concentration etc..Therefore, because that there are equipment investments is high, big for this method
Organic solvent of the amount using energy and for dissolving anthraquinone is discharged to atmosphere, so being not necessarily the system of ideal hydrogen peroxide
Make method.
As solution to the problems described above, has and directly manufacture peroxide from oxygen and hydrogen using catalyst in reaction medium
Change the method for hydrogen.For example, propose in the presence of water, acid and organic compound containing non-acid oxygen with liquid phase make hydrogen and
The method that oxygen contains gold, the solid catalyst of platinum or palladium contacts and manufacture hydrogen peroxide with as metal component, it is known that generate
Hydrogen peroxide (patent document 1) to a certain degree.
A kind of method for contiguously manufacturing hydrogen peroxide from hydrogen and oxygen in reaction medium is disclosed in patent document 2,
In, hydrogen peroxide is manufactured using the platinum metal catalysts for being supported at oxide carrier.In the document, about reaction medium, report
Road water is usually suitable, in order to inhibit the decomposition of the hydrogen peroxide generated, can suitably use aqueous hydrochloric acid solution, hydrobromic acid
Aqueous solution, phosphate aqueous solution, aqueous sulfuric acid etc., particularly aqueous hydrochloric acid solution, hydrobromic acid aqueous solution.It can also in addition, describing
It is enough to be suitably employed as the mixing waters such as sodium chloride, potassium chloride of chloride ion ingredient etc. and sulfuric acid, phosphoric acid as hydrogen ion ingredient
The combination of solution replaces aqueous hydrochloric acid solution.In addition, describing sodium bromide, the bromine that can also be suitably employed as bromide ion ingredient
Change the combination of the mixed aqueous solution of potassium etc. and the sulfuric acid as hydrogen ion ingredient, phosphoric acid etc. to replace hydrobromic acid aqueous solution.
Proposed in patent document 3 it is a kind of in the stirred type reactor directly from hydrogen and oxygen manufacture aqueous hydrogen peroxide solution
Method, wherein make hydrogen and oxygen is respectively small bubble shape, add inorganic acid and be set as acid in advance and by the importing of hydrogen and oxygen
Amount is set as certain molar ratio.The document, which also describes above-mentioned aqueous reaction medium, may include stabilizer for hydrogen peroxide
(for example, phosphonate ester or tin) and decomposing inhibitor (for example, halide).In addition, above-mentioned document describes bromide in halide
For particularly preferred decomposing inhibitor, advantageously with the bromine (Br of free state2) be applied in combination.
A kind of organic hydrogen peroxide solutions based on direct synthesis technique or organic hydroperoxide water are disclosed in patent document 4
The autofrettage of solution, at this point, making unexplosive gasiform mixture and liquid reaction medium containing hydrogen and oxygen to by wrapping
The fixed bed conducting that mixture containing noble metal catalyst is constituted.The document also discloses that aforesaid liquid reaction medium contains strong acid
And halide.
A kind of peroxide from hydrogen and oxygen, using the heterogeneous catalysis effect in three-phase system is disclosed in patent document 5
Change the direct synthesis method of the aqueous solution of hydrogen, wherein in the solid heterogeneous catalysis being suspended in liquid water phase with plastochondria state
The surface of agent is directly reacted, and the catalyst is by the combined metallic compound selected from pure palladium or palladium and at least one other noble metal
It constitutes.In addition, the document discloses above-mentioned metallic compounds in the method to be supported at comprising selected from zirconium dioxide and hyper acidic
It is risen on the carrier of at least one compound of zirconium dioxide, in aforesaid liquid water phase with 0.05~3mmol/ relative to water phase dense
Degree contains bromide ion, and its pH is in 0~4 range.
A kind of peroxidating method for preparing hydrogen is disclosed in patent document 6 and 7, wherein without using halogen ion as decomposition
Inhibitor in reaction medium reacts in the presence of noble metal catalyst and free radical scavenger hydrogen and oxygen.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Publication 40-19006 bulletin
Patent document 2: No. 3394043 bulletins of Japanese Patent No.
Patent document 3: Japanese Unexamined Patent Application Publication 2002-503617 bulletin
Patent document 4: Japanese Unexamined Patent Application Publication 2007-537119 bulletin
Patent document 5: Japanese Unexamined Patent Publication 05-213607 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2014-15353 bulletin
Patent document 7: International Publication No. 2014/01372
Summary of the invention
Problems to be solved by the invention
But the direct autofrettage of such existing hydrogen peroxide cannot obtain the hydrogen peroxide of high concentration, become
Practical one of project.
The method used for solving the problem
The present inventor furthers investigate, as a result, it has been found that, by obtaining peroxide and reacting hydrogen and oxygen directly
Change in the method for hydrogen using the noble metal catalyst with specific composition, the manufacture of the hydrogen peroxide of high concentration may be implemented, from
And complete the present invention.
That is, the specific scheme for solving the above subject is as described below.
First embodiment of the invention be it is a kind of react hydrogen and oxygen directly and obtain hydrogen peroxide method in use
Noble metal catalyst, wherein
Comprising palladium, gold, oxygen atom and bromine atom, above-mentioned oxygen atom and bromine atom are present in the most appearance of noble metal catalyst
Face.
Second embodiment of the invention is a kind of peroxidating method for preparing hydrogen comprising:
The step of including the gas of hydrogen and oxygen is imported in reaction medium；With
In reaction medium, make the hydrogen imported and the noble metal catalyst of oxygen and above-mentioned first embodiment 0.1MPa with
On pressure under the step of contacting and obtaining hydrogen peroxide.
The effect of invention
By using noble metal catalyst of the invention, in the method for reacting hydrogen and oxygen directly and obtaining hydrogen peroxide
In, the hydrogen peroxide of high concentration can be manufactured.In addition, peroxidating method for preparing hydrogen through the invention, can manufacture highly concentrated
The hydrogen peroxide of degree.
Specific embodiment
Hereinafter, noble metal catalyst of the invention and peroxidating method for preparing hydrogen are described in detail.In addition, at this
In specification, the hydrogen peroxide of high concentration refers to the hydrogen peroxide of such as 5 weight % or more, more preferable 10 weight % or more.
Embodiment 1: noble metal catalyst
Noble metal catalyst of the invention includes palladium, gold, oxygen atom and bromine atom, and above-mentioned oxygen atom and bromine atom are present in
The outmost surface of noble metal catalyst.
Noble metal catalyst of the invention includes that palladium and gold are used as noble metal.The molar ratio (palladium/gold) of palladium and gold is preferably
0.1~10, more preferably 1~5.Noble metal catalyst of the invention in addition to palladium and gold other than, also can wrap platiniferous or silver etc. its
Its noble metal.In addition, in the present note, will not include yet the state of oxygen atom and bromine atom, include your gold of palladium and gold
It is called as precious metal catalyst precursor.
In order to improve catalytic efficiency and reaction efficiency, noble metal can be made to be supported at carbon, silica, aluminium oxide, dioxy
The carriers such as SiClx aluminium oxide, titanium oxide or zirconium oxide.As carrier, it is preferable to use Titanium Dioxide Rutile Top grade.
As the method that above-mentioned noble metal is supported at carrier, conventionally known side is used without special limitation
Method, preferably impregnated with method or ion-exchange.As above-mentioned impregnated with method, can be filled out using solid method, Equilibrium Adsorption Method, hole is evaporated
Fill method etc..
About above-mentioned noble metal in the loading amount of carrier, relative to 100 parts by weight of carrier, noble metal is preferably 0.01~10
Parts by weight, more preferably 0.05~5 parts by weight.Also, it in peroxidating method for preparing hydrogen of the invention, is urged about noble metal
The usage amount of agent (being carrier catalyst in the case where being supported at carrier), is 1~100g preferably with respect to reaction medium 1L, more
It is 1~40g preferably with respect to 1L.
Noble metal can not also be supported at and monolithically use, for example, also can so that noble metal dispersion in polyvinyl pyrrole
The state of nano-colloid in the dispersing agents such as pyrrolidone uses.
There are oxygen atoms and bromine atom in its outmost surface for noble metal catalyst of the invention." exist in its outmost surface
Oxygen atom and bromine atom " refers to the outermost in noble metal catalyst, and there are oxygen atoms and bromine atom, but are not precluded within noble metal
There are oxygen originals there are the atom other than oxygen atom and bromine atom and on the inside of noble metal catalyst for the outmost surface of catalyst
Son and bromine atom.By making noble metal catalyst of the invention in its outmost surface, there are oxygen atoms and bromine atom, should using
In the peroxidating method for preparing hydrogen of noble metal catalyst, the manufacture of the hydrogen peroxide of high concentration can be realized.Using existing
Noble metal catalyst from the method that oxygen and hydrogen directly manufacture hydrogen peroxide, above-mentioned catalyst is also used as the decomposition of hydrogen peroxide
Catalyst works, and therefore, also causes the decomposition of hydrogen peroxide generated simultaneously.Therefore, in such method, most of
In the case of, in order to inhibit decompose and use certain compounds, it is known in the art that make the halogen such as chloride ion or bromide ion from
Son is present in the liquid phase of reaction medium.But it is still unknown as noble metal catalyst of the invention in noble metal catalyst
There are the structures of oxygen atom and bromine atom for itself.The present inventor's first discovery knot of noble metal catalyst of the invention
Structure finds under conditions of there are noble metal catalyst of the invention, realizes the manufacture of the hydrogen peroxide of high concentration.As its machine
System, is still not clear, it is believed that noble metal catalyst of the invention is by the way that in its outmost surface, there are oxygen atom and bromine are former
Son, manufactured hydrogen peroxide is suppressed to adsorbing again for noble metal catalyst, and the decomposition of hydrogen peroxide is suppressed, as knot
The manufacture concentration of fruit, hydrogen peroxide increases.
It can be analyzed by low-energy ion scattering (Low Energy Ion Scattering:LEIS) to confirm oxygen atom
It is present in the outmost surface of noble metal catalyst with bromine atom.Low-energy ion scattering (LEIS) analytic approach is irradiated to the surface of solids
Number 100eV~rare gas of the number keV or ion beam of alkali element, measure the power spectrum and angular spectrum of the ion of scattering, thus divides
The method for analysing sample is able to carry out the qualitative, quantitative of outermost surface layer atom.As low-energy ion scattering light-dividing device (LEIS),
For example, being able to use the Qtac100 of ION-TOF company manufacture.
In noble metal catalyst of the invention, by low-energy ion scattering (LEIS) analysis measurement bromine atom relative to
The ratio between detection limit of palladium is preferably 0.10 or more, more preferably 0.15 or more, more preferably 0.3 or more.In addition, by low energy from
The ratio between detection limit relative to palladium of bromine atom of son scattering (LEIS) analysis measurement preferably 0.45 hereinafter, more preferably 0.40 with
Under.The ratio between detection limit by the bromine atom of the low-energy ion scattering (LEIS) analysis measurement relative to palladium is preferably in aftermentioned mistake
Oxidation method for preparing hydrogen during keep certain value, since directly reacts hydrogen and oxygen to react terminate between variation
Amount is preferably Δ 0.5 hereinafter, more preferably Δ 0.30 is hereinafter, more preferably 0.25 or less Δ.By in noble metal catalyst
There are the bromines of the specific quantity for outmost surface, can manufacture the hydrogen peroxide of high concentration.
In noble metal catalyst of the invention, by low-energy ion scattering (LEIS) analysis measurement oxygen atom relative to
The ratio between palladium is preferably 1.5 or more, more preferably 1.7 or more.In addition, former by the oxygen of low-energy ion scattering (LEIS) analysis measurement
Son is preferably 4.0 hereinafter, more preferably 3.5 or less relative to the ratio between palladium.It is considered that by being present in oxygen atom with the amount
The outmost surface of noble metal catalyst, palladium becomes the state of oxidation, as a result, bromine atom is easy to be present in noble metal catalyst
Outmost surface.The ratio between detection limit by the oxygen atom of the low-energy ion scattering (LEIS) analysis measurement relative to palladium is preferably rear
Do not change during the peroxidating method for preparing hydrogen stated or micro- increasing, more preferably with the increasing of every 1 hour 0~0.25 variable quantity
Add, more preferably increased with the variable quantity of every 1 hour Δ 0~0.1, is preferably increased with the variable quantity of every 1 hour Δ 0~0.05.It can
To think the oxygen atom by making noble metal catalyst outmost surface during completing since directly reacting hydrogen and oxygen to reaction
Amount do not change or micro- increasing, the phase is also able to maintain that the decomposition of hydrogen peroxide inhibits after the reaction, manufactures the hydrogen peroxide of high concentration.
By the way that bromine ingredient is excessively added in reaction medium, similar effect is obtained, but by the way that the surface of noble metal catalyst to be set as
The state of oxidation can efficiently maintain the adsorbance of bromine atom.
Noble metal catalyst of the invention can by make precious metal catalyst precursor in the medium with oxygen ingredient and bromine at
Tap touching is to manufacture.Wrap oxygen containing gas for example, importing in the liquid phase medium comprising bromine ingredient, make bromine in liquid phase medium at
The oxygen and precious metal catalyst precursor divide, imported contacts under the pressure of 0.1MPa or more, and thereby, it is possible to obtain precious metal catalyst
Agent.Partial pressure of oxygen in the gas of importing is preferably 20% or more, and more preferably 30% or more, more preferably 40% or more, it is more excellent
It is selected as 50% or more, more preferably 60% or more, more preferably 70% or more, more preferably 80% or more.Gas as importing
The upper limit of partial pressure of oxygen in body, it can be considered that it is 95%, 90% etc. that the partial pressure of other gas componants, which is suitably set,.The gas of importing
In addition to oxygen, hydrogen, nitrogen, argon gas, helium or carbon dioxide also may include.Liquid phase medium can enumerate water, methanol, second
The ketone such as the alcohol such as alcohol, acetone and their mixed solvent, among these, preferably water and alcohol.As bromine ingredient, bromine can be enumerated
The bromides such as acid, bromate, sodium bromide, among these, preferred sodium bromide.The usage amount of bromine ingredient is preferably in reaction medium
0.01mM~10mM, more preferably 0.02mM~5mM, further preferably 0.02mM~1mM.The pressure of reaction is preferably
0.1MPa~10MPa, more preferably 0.5MPa~5MPa, further preferably 1MPa~2MPa.In addition, the reaction time is usually
0.01~100 hour, preferably 0.5~10 hour.
Noble metal catalyst of the invention can by the peroxidating method for preparing hydrogen of aftermentioned embodiment 2, with
The mode prepared when will use manufactures.For example, adding above-mentioned noble metal catalyst in the reaction medium comprising bromine ingredient
Precursor contacts the oxygen imported and precious metal catalyst precursor under the pressure of 0.1MPa or more, thus, it is possible to
It is enough that noble metal catalyst is manufactured in reaction system.Moreover, can using the state directly in the manufacturing process of hydrogen peroxide as
Noble metal catalyst for reacting hydrogen and oxygen directly and obtaining hydrogen peroxide uses.
In addition, noble metal catalyst of the invention reacts the hydrogen peroxide of the high concentration in later period by being supported at carrier
Inhibitory effect is decomposed to improve, so it is preferred that.
Embodiment 2: peroxidating method for preparing hydrogen
Peroxidating method for preparing hydrogen of the invention includes:
The step of including the gas of hydrogen and oxygen is imported in reaction medium；With
Make in reaction medium the hydrogen imported and the noble metal catalyst of oxygen and above-mentioned first embodiment 0.1MPa with
On pressure under contact and obtain hydrogen peroxide the step of.Peroxidating method for preparing hydrogen through the invention, can manufacture
The hydrogen peroxide of high concentration.
The noble metal catalyst used in peroxidating method for preparing hydrogen of the invention is above-mentioned first embodiment
Noble metal catalyst.Accordingly, with respect to above-mentioned duplicate record, appropriate omit record.In the system of hydrogen peroxide of the invention
It makes in method, the usage amount of noble metal catalyst (being carrier catalyst in the case where being supported at carrier) is preferably with respect to reaction
Medium 1L is 1~100g, is more preferably 1~40g relative to 1L.
In peroxidating method for preparing hydrogen of the invention, the partial pressure of oxygen in the gas of importing is preferably 20% or more, more
Preferably 30% or more, more preferably 40% or more, more preferably 50% or more, more preferably 60% or more, more preferably
70% or more, more preferably 80% or more.As the upper limit of the partial pressure of oxygen in the gas of importing, it can be considered that other gas componants
Partial pressure to suitably set be 95%, 90% etc..By making the partial pressure of oxygen aforementioned proportion in the gas imported, manufacture can be increased
Hydrogen peroxide concentration.It as its mechanism, is still not clear, it is believed that by increasing oxygen on noble metal catalyst surface
Amount can be improved the speed of hydrogen peroxide generation.
In addition, in the case that the partial pressure of oxygen in the gas imported is aforementioned proportion, by being situated between in the reaction comprising bromine ingredient
Above-mentioned precious metal catalyst precursor is added in matter, and imported hydrogen and oxygen and precious metal catalyst precursor are made in reaction medium
It is contacted under the pressure of 0.1MPa or more, it is real that above-mentioned first can be manufactured in a manner of preparing when that will use in reaction system
The noble metal catalyst of mode is applied, the noble metal catalyst for making hydrogen and oxygen and first embodiment can be directly carried out with the state
The process for being contacted under the pressure of 0.1MPa or more and obtaining hydrogen peroxide, so it is preferred that.
Hydrogen partial pressure in the gas of importing be preferably avoid explosive range and oxygen relative to excess hydrogen ratio (for example, hydrogen
The volume ratio of the flow of gas and oxygen becomes the ratio of 1 ︰, 2~1 ︰ 10), for example, 5~20%, preferably 10~15%.Into
One step considers from a security point, further decreases the risk of explosion, it is therefore preferable that diluting hydrogen and oxygen.At this time can
The diluent gas enough used is the inactive gas not affected to the reaction of hydrogen and oxygen, for example, being able to use nitrogen, argon gas
And helium.From the aspect of cost, preferred nitrogen.In addition, oxygen can also use compressed air to be diluted and mix as oxygen
Gas uses.In addition, also may include carbon dioxide in gas, the carbon dioxide partial pressure for example, 0.01 in gas at this time~
5%, preferably 1~2%.
Gas comprising hydrogen and oxygen is imported into reaction medium, from the aspect of reaction efficiency, is normally introduced into liquid phase, i.e.
In reaction solution.
In peroxidating method for preparing hydrogen of the invention, reaction medium preferably comprises bromine ingredient.It, can be with as bromine ingredient
The bromides such as bromic acid, bromate, sodium bromide are enumerated, among these, preferred sodium bromide.The case where reaction medium includes bromine ingredient
Under, above-mentioned precious metal catalyst precursor is added in reaction medium, makes 20% or more the partial pressure importeding into reaction medium
Oxygen contacts under the pressure of 0.1MPa or more with precious metal catalyst precursor, thereby, it is possible in reaction system will use
When the mode for preparing manufacture the noble metal catalyst of above-mentioned first embodiment, can directly carry out making with the state hydrogen and oxygen with
The noble metal catalyst of first embodiment contacts under the pressure of 0.1MPa or more and the process that obtains hydrogen peroxide, so it is excellent
Choosing.
The usage amount of bromine ingredient is 0.01mM~10mM, more preferably 0.02mM~5mM preferably in reaction medium, into one
Step is preferably 0.02mM~1mM.
In peroxidating method for preparing hydrogen of the invention, in order to inhibit the decomposition of hydrogen peroxide, also it can be used at present
Halogen or halogen ion (for example, chlorine or chloride ion) other than the bromine used.
Peroxidating method for preparing hydrogen of the invention is implemented in the reaction medium of usually liquid phase.As long as reaction medium is not
The reaction for interfering hydrogen and oxygen is used without special limitation.Such reaction medium is those skilled in the art's public affairs
Know.
As the example of above-mentioned reaction medium, the ketone such as the alcohol such as water, methanol, ethyl alcohol, acetone can be enumerated and theirs is mixed
Bonding solvent.Among these, preferably water and alcohol.Alternatively, it is also possible to by water solubility be 0.1g/L heptane below, hexane, pentane
Equal hydrocarbon solvents, the fluorine system liquid with perfluocarbon construction are as secondary solvent.
In addition, in these reaction mediums may be pH adjusting, stabilizer effect or gaseous solubility raising etc. and contained
There is additive, for example, it is also possible to contain the acid such as phosphoric acid, sulfuric acid and fluorine system torpescence liquid etc..Contain these in reaction medium to add
In the case where adding object, the weight of reaction medium is the weight for including additive.
These reaction mediums also contain free radical scavenger.As free radical scavenger, as long as with radical-scavenging
Function can be arbitrary agent for capturing, for example, carbon dioxide can be enumerated, in Japanese Unexamined Patent Publication 2014-15353 bulletin
Illustrated by nitronic acid compound, nitroso compound, dithiocarbamate derivative and ascorbic acid derivates.These
Free radical scavenger may be the form of salt, in addition, in the case where that can be hydrate, or the form.As
Above-mentioned salt can enumerate sodium salt, sylvite etc..
In the present invention, the noble metal catalyst of the hydrogen imported and oxygen and above-mentioned first embodiment is made in reaction medium
It is contacted under the pressure of 0.1MPa or more and obtains hydrogen peroxide.
In the reaction, by being set as high pressure, the hydrogen concentration and oxygen concentration that molten can be stored in water, energy can be increased
The yield of hydrogen peroxide is enough improved, therefore, it is possible to use there are the reaction units such as autoclave of usual resistance to pressure to implement.
Above-mentioned reaction unit is able to use any types such as stirring groove profile, bubble-column-type, fixed-bed type, microreactor,
In addition, reaction can either be carried out by batch type or continous way.Above-mentioned reaction unit has gas introduction part and gas discharge section,
In general, also having thermometer and pressure gauge etc..
In addition, in the reaction of the present invention, due to also using corrosive halogen sometimes, it is preferred as reaction unit
Use stainless steel, alray (Inconel) or the heat-proof corrosion-resistant nickel-base alloy by Teflon (registered trademark) lining
(Hastelloy) device formed.Also the reaction unit formed by stainless steel, enamel can be used.
In the present invention, preferably 0~100 DEG C of reaction temperature of hydrogen and oxygen when hydrogen peroxide synthesizes, particularly preferred 5~50
DEG C range.The pressure of reaction is 0.1MPa or more, preferably 0.1MPa~10MPa, more preferably 0.5MPa~5MPa, into one
Step is preferably 1MPa~2MPa.In addition, the reaction time is usually 0.01~100 hour, preferably 0.5~50 hour.
Peroxidating method for preparing hydrogen of the invention includes:
Packet is imported in such a way that the partial pressure of oxygen in the gas of importing is 20% or more in the reaction medium comprising bromine ingredient
The step of hydrogeneous and oxygen gas；
In reaction medium, connect the oxygen imported under the pressure of 0.1MPa or more with above-mentioned precious metal catalyst precursor
The step of touching and obtaining noble metal catalyst；With
In reaction medium, make import hydrogen and oxygen with by above-mentioned operation obtain noble metal catalyst 0.1MPa with
On pressure under the step of contacting and obtaining hydrogen peroxide.It, can be in reaction system when system will be being used according to which
Standby mode manufactures the noble metal catalyst of above-mentioned first embodiment, can be with the state directly there are noble metal catalysts
Under conditions of carry out it is next obtain hydrogen peroxide process, so it is preferred that.In this approach, the amount, partial pressure of oxygen of bromine ingredient,
As the reaction conditions such as reaction pressure are as defined above.
In peroxidating method for preparing hydrogen of the invention, noble metal catalyst is analyzed by low-energy ion scattering (LEIS)
The ratio between the detection limit of the bromine atom of measurement relative to palladium be preferably 0.10 or more, more preferably 0.15 or more, more preferably 0.3 with
On.In addition, the ratio between the detection limit by the bromine atom of low-energy ion scattering (LEIS) analysis measurement relative to palladium is preferably 0.45
Hereinafter, more preferably 0.40 or less.Detection by the bromine atom of the low-energy ion scattering (LEIS) analysis measurement relative to palladium
The ratio between amount preferably keeps certain value during peroxidating method for preparing hydrogen, to reaction since directly reacting hydrogen and oxygen
Variable quantity during completion is preferably Δ 0.5 hereinafter, more preferably Δ 0.3 is hereinafter, more preferably 0.25 or less Δ.By
Outmost surface during being completed since directly reacting hydrogen and oxygen to reaction in noble metal catalyst there are the bromine of the specific quantity,
The hydrogen peroxide of high concentration can be manufactured.
In peroxidating method for preparing hydrogen of the invention, noble metal catalyst is analyzed by low-energy ion scattering (LEIS)
The oxygen atom of measurement is preferably 1.5 or more, more preferably 1.7 or more relative to the ratio between palladium.In addition, passing through low-energy ion scattering
(LEIS) oxygen atom of analysis measurement is preferably 4.0 hereinafter, more preferably 3.5 or less relative to the ratio between palladium.It is considered that passing through
Oxygen atom is set to be present in the outmost surface of noble metal catalyst with the amount, palladium becomes the state of oxidation, as a result, bromine atom is easy
It is present in the outmost surface of noble metal catalyst.By the oxygen atom of the low-energy ion scattering (LEIS) analysis measurement relative to palladium
The ratio between detection limit preferably do not change during peroxidating method for preparing hydrogen or micro- increasing, more preferably with every 1 hour 0~
0.25 variable quantity increases, and is more preferably increased with the variable quantity of every 1 hour Δ 0~0.1, preferably with every 1 hour Δ 0~0.05
Variable quantity increases.It is considered that by starting the direct reaction since hydrogen and oxygen to noble metal catalyst during reacting completion most
The amount of the oxygen atom of outer surface does not change or micro- increasing, and the phase is also able to maintain that the decomposition of hydrogen peroxide inhibits after the reaction, can make
Make the hydrogen peroxide of high concentration.By the way that bromine ingredient is excessively added in reaction medium, similar effect is obtained, but by by your gold
The surface of metal catalyst is set as the state of oxidation, can efficiently maintain the adsorbance of bromine atom.
Embodiment
Hereinafter, further illustrating the present invention based on embodiment and comparative example, but the present invention is not limited to implementations below
Example.
(embodiment 1)
(1) carrier holds the manufacture of noble metal catalyst
Oxalic acid 2g is added in the mixed solvent 200ml (water ︰ ethyl alcohol=1 ︰ 1) of second alcohol and water and is stirred.Thereto
Add Sakai chemistry titanium dioxide (Titanium Dioxide Rutile Top grade (IV)) 10g, HAuCl40.05g and PdCl20.12g uses Lee's ratio
Uncommon condenser, while flowing back 1 hour at 80 DEG C.
After 1 hour, aaerosol solution is moved on in 300ml beaker, is heated and removes solvent.Then, make what is obtained to consolidate
Body is 1 day dry in 85 DEG C of drying machines, obtains carrier and holds precious metal catalyst precursor (Pd-Au/TiO2)。
Then, to the high pressure with agitating device and the 270ml with Teflon (registered trademark) liner of gas insufflation tube
The carrier that above-mentioned manufacture is added in kettle holds precious metal catalyst precursor (Pd-Au/TiO2) 1.125g, reaction solution 270ml
(containing 0.5mM phosphoric acid and 0.05mM sodium bromide, reaction medium is water).
While high pressure temperature in the kettle is adjusted to 25 DEG C, while by gas with 250ml/min (hydrogen 10%, oxygen 80%, nitrogen 10%)
Speed be blown into autoclave (partial pressure of oxygen 80% in gas) and stirred while pressure is adjusted to 1M Pascal with revolving speed 1000rpm
It mixes, while making its reaction, manufactures noble metal catalyst.During the reaction, hydrogen peroxide has also been manufactured.In reaction solution
Import precious metal catalyst precursor after, noble metal catalyst is taken out from reaction solution in per certain time, by low energy from
Son scattering (LEIS) analysis measures the surface of the noble metal catalyst in each reaction time.In addition, being within the reaction time 0 hour in table 1
Refer to the state for taking out noble metal catalyst at once after reaction solution imports precious metal catalyst precursor.
(surface analysis of noble metal catalyst)
The surface analysis of noble metal catalyst carries out as described below.
Low-energy ion scattering light-dividing device (LEIS) Qtac100 (ION-TOF corporation) is being utilized, in 2KeV~5KeV
Helium ion or ne ion beam irradiation under conditions of, carry out noble metal catalyst surface elemental analysis.In the power spectrum of acquisition
Identify each element.Calculate each element detection limit (integrated value), find out the ratio between detection limit of the bromine atom relative to palladium (Br/Pd) with
And the ratio between the detection limit of oxygen atom relative to palladium (O/Pd).The ratio between these detection limits are indicated in table 1.
(embodiment 2)
In addition to the composition of the gas of embodiment 1 is changed to the gas composition of hydrogen 10%, oxygen 18%, nitrogen 72% (in gas
Partial pressure of oxygen 18%) other than, operate similarly to Example 1, manufacture noble metal catalyst, pass through low-energy ion scattering (LEIS) point
Analysis measures the surface of the noble metal catalyst in each reaction time.Result is indicated in table 1.Peroxide has also been manufactured during reaction
Change hydrogen.
[table 1]
| Partial pressure of oxygen (%) | Reaction time (hr) | Br/Pd | O/Pd |
| 80 | 0 | 0.352 | 1.95 |
| 80 | 2 | 0.327 | 2.45 |
| 80 | 16 | 0.159 | 3.36 |
| 18 | 0 | 0.001 | 1.25 |
| 18 | 2 | 0.498 | 0.71 |
| 18 | 8 | 0.295 | 1.02 |
| 18 | 11 | 0.203 | - |
| 18 | 14 | 0.248 | 0.97 |
As known to the result shown in the table 1, it is thus identified that in the outmost surface of noble metal catalyst, there are oxygen atoms and bromine
Atom.In addition, the ratio between detection limit in bromine atom relative to palladium is 0.10 or more and oxygen atom relative to the ratio between palladium is 1.5 or more
In the case where, the hydrogen peroxide of higher concentration has been manufactured in the reaction.
(embodiment 3)
(1) carrier holds the manufacture of precious metal catalyst precursor
Oxalic acid 2g is added in the mixed solvent 200ml (water ︰ ethyl alcohol=1 ︰ 1) of second alcohol and water and is stirred.Thereto
Add Sakai chemistry titanium dioxide (Titanium Dioxide Rutile Top grade (IV)) 10g, HAuCl40.05g and PdCl20.12g uses Lee's ratio
Uncommon condenser, while flowing back 1 hour at 80 DEG C.
After 1 hour, aaerosol solution is moved on in 300ml beaker, is heated and removes solvent.Then, make what is obtained to consolidate
Body is 1 day dry in 85 DEG C of drying machines, obtains carrier and holds precious metal catalyst precursor (Pd-Au/TiO2)。
(2) manufacture of hydrogen peroxide
In an experiment, to the 270ml's with Teflon (registered trademark) liner with agitating device and gas insufflation tube
The carrier that above-mentioned manufacture is added in autoclave holds precious metal catalyst precursor (Pd-Au/TiO2) 1.125g, reaction solution
270ml (containing 0.5mM phosphoric acid and 0.05mM sodium bromide, reaction medium is water).
While high pressure temperature in the kettle is adjusted to 25 DEG C, while by gas with 250ml/min (hydrogen 10%, oxygen 25%, nitrogen 64%,
Carbon dioxide 1%) speed be blown into autoclave (partial pressure of oxygen 25% in gas), while pressure is adjusted to 1M Pascal, with
Revolving speed 1000rpm stirring, while making its reaction.After importing precious metal catalyst precursor in reaction solution, make in per certain time
With hydrogen peroxide automatic titration device, (device name: HP-300, manufacturing company: flat natural pond industry uses iodine coulometric titration
Mensuration mode) concentration of hydrogen peroxide is quantified, after confirmation concentration of hydrogen peroxide starts reduction, terminate reaction.Peroxide
The peak value for changing hydrogen concentration occurs after reaction starts 30 hours, is 6.0wt%.Result is indicated in table 2.
During above-mentioned hydrogen peroxide manufacture, carrier is also manufactured and has held noble metal catalyst.
(embodiment 4)
In addition to the composition by the gas of embodiment 3 is changed to the gas of hydrogen 10%, oxygen 30%, nitrogen 59%, carbon dioxide 1%
It forms other than (partial pressure of oxygen 30% in gas), operates similarly to Example 3, manufacture hydrogen peroxide.Concentration of hydrogen peroxide
Peak value occurs after reaction starts 45 hours, is 7.7wt%.
(embodiment 5)
In addition to the composition by the gas of embodiment 3 is changed to the gas of hydrogen 10%, oxygen 50%, nitrogen 39%, carbon dioxide 1%
It forms other than (partial pressure of oxygen 50% in gas), operates similarly to Example 3, manufacture hydrogen peroxide.Concentration of hydrogen peroxide
Peak value occurs after reaction starts 30~40 hours, is 9.0wt%.
(embodiment 6)
In addition to the composition by the gas of embodiment 3 is changed to the gas of hydrogen 10%, oxygen 70%, nitrogen 19%, carbon dioxide 1%
It forms other than (partial pressure of oxygen 70% in gas), operates similarly to Example 3, manufacture hydrogen peroxide.Concentration of hydrogen peroxide
Peak value occurs after reaction starts 40 hours, is 11.0wt%.
(embodiment 7)
In addition to the composition by the gas of embodiment 3 is changed to the gas composition (gas of hydrogen 10%, oxygen 89%, carbon dioxide 1%
Partial pressure of oxygen 89% in body) other than, it operates similarly to Example 3, manufactures hydrogen peroxide.The peak value of concentration of hydrogen peroxide is anti-
Occur after should starting 45 hours, is 11.5wt%.
(comparative example 1)
In addition to the composition of the gas of embodiment 3 is changed to hydrogen 10%, oxygen 19.2%, nitrogen 69.8%, carbon dioxide 1%
It other than gas composition (partial pressure of oxygen 19.2% in gas), operates similarly to Example 3, manufactures hydrogen peroxide.Hydrogen peroxide
The peak value of concentration occurs after reaction starts 25 hours, is 4.7wt%.
(embodiment 8)
(1) manufacture of nano-colloid precious metal catalyst precursor
Polyvinylpyrrolidone (PVP) as dispersing agent and is restored into PdCl by oxalic acid2And HAuCl4, prepare nanometer
Colloid precious metal catalyst precursor (Pd-Au nano-colloid).
(2) manufacture of hydrogen peroxide
In an experiment, to the 270ml's with Teflon (registered trademark) liner with agitating device and gas insufflation tube
Nano-colloid precious metal catalyst precursor (Pd-Au nano-colloid) 74.52mg, the reaction that above-mentioned manufacture is added in autoclave are molten
Liquid 130ml (containing 0.5mM phosphoric acid and 2.0mM sodium bromide, reaction medium is water and ethyl alcohol).
While high pressure temperature in the kettle is adjusted to 20 DEG C, while by gas with 600ml/min (hydrogen 10%, oxygen 30%, nitrogen 60%)
Speed be blown into autoclave (partial pressure of oxygen 30% in gas), while pressure is adjusted to 1M Pascal, stirred with revolving speed 1000rpm
It mixes, while making its reaction.It is automatic using hydrogen peroxide in per certain time after importing precious metal catalyst precursor in reaction solution
Titration outfit (device name: HP-300, manufacturing company: flat natural pond industry uses the measurement method of iodine coulometric titration) is to peroxide
Change hydrogen concentration to be quantified, after confirmation concentration of hydrogen peroxide starts reduction, terminates reaction.The peak value of concentration of hydrogen peroxide is anti-
Occur after should starting 8 hours, is 7.0wt%.Result is indicated in table 3.
(embodiment 9)
In addition to the composition by the gas of embodiment 8 is changed to the gas of hydrogen 10%, oxygen 60%, nitrogen 29%, carbon dioxide 1%
It forms other than (partial pressure of oxygen 60% in gas), operates similarly to Example 8, manufacture hydrogen peroxide.Concentration of hydrogen peroxide
Peak value occurs after reaction starts 8 hours, is 8.0wt%.
(embodiment 10)
In addition to the composition by the gas of embodiment 8 is changed to the gas of hydrogen 10%, oxygen 80%, nitrogen 9%, carbon dioxide 1%
It forms other than (partial pressure of oxygen 80% in gas), operates similarly to Example 8, manufacture hydrogen peroxide.Concentration of hydrogen peroxide
Peak value occurs after reaction starts 14 hours, is 10.0wt%.
[table 2]
| Partial pressure of oxygen (%) | H2O2Concentration (wt%) | |
| Embodiment 3 | 25 | 6.0 |
| Embodiment 4 | 30 | 7.7 |
| Embodiment 5 | 50 | 9.0 |
| Embodiment 6 | 70 | 11.0 |
| Embodiment 7 | 89 | 11.5 |
| Comparative example 1 | 19.2 | 4.7 |
[table 3]
| Partial pressure of oxygen (%) | H2O2Concentration (wt%) | |
| Embodiment 8 | 30 | 7.0 |
| Embodiment 9 | 60 | 8.0 |
| Embodiment 10 | 80 | 10.0 |
As known to the result shown in the table 2 and table 3, peroxidating method for preparing hydrogen of the invention can manufacture high concentration
Hydrogen peroxide.In addition, knowing: in peroxidating method for preparing hydrogen, the partial pressure of oxygen in gas imported by control can
Noble metal catalyst of the invention is obtained, while peroxidating can be carried out under conditions of there are noble metal catalyst of the invention
The manufacture of hydrogen obtains the hydrogen peroxide of high concentration.
Claims (6)
1. a kind of noble metal catalyst, react hydrogen and oxygen directly and obtain hydrogen peroxide method in use, it is described expensive
Metallic catalyst is characterized in that:
Comprising palladium, gold, oxygen atom and bromine atom, the oxygen atom and bromine atom are present in the outmost surface of noble metal catalyst.
2. noble metal catalyst as described in claim 1, it is characterised in that:
The ratio between detection limit by the bromine atom of low-energy ion scattering (LEIS) analysis measurement relative to palladium is 0.10 or more.
3. noble metal catalyst as claimed in claim 1 or 2, it is characterised in that:
The oxygen atom measured by low-energy ion scattering (LEIS) analysis is 1.5 or more relative to the ratio between palladium.
4. a kind of peroxidating method for preparing hydrogen characterized by comprising
The step of including the gas of hydrogen and oxygen is imported in reaction medium；With
In reaction medium, the hydrogen imported and oxygen and noble metal catalyst according to any one of claims 1 to 3 is made to exist
The step of contacting under the pressure of 0.1MPa or more and obtain hydrogen peroxide.
5. manufacturing method as claimed in claim 4, it is characterised in that:
Partial pressure of oxygen in the gas of importing is 20% or more.
6. peroxidating method for preparing hydrogen as described in claim 4 or 5, it is characterised in that:
Reaction medium includes bromine ingredient.
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| JP2016141392 | 2016-07-19 | ||
| JP2016-141392 | 2016-07-19 | ||
| PCT/JP2017/025067 WO2018016359A1 (en) | 2016-07-19 | 2017-07-10 | Noble metal catalyst for manufacturing hydrogen peroxide, and method for manufacturing hydrogen peroxide |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038437A (en) * | 1988-05-13 | 1990-01-03 | 纳幕尔杜邦公司 | Use preferred H +And Br -Concentration is produced the method for hydrogen peroxide |
| JPH04360848A (en) * | 1991-06-05 | 1992-12-14 | Takasago Internatl Corp | Production of cyclic mono-or sesquiterpene ketone |
| CA2338104A1 (en) * | 2000-02-26 | 2001-08-26 | Degussa Ag | Method of producing hydrogen peroxide by direct synthesis and noble-metal catalyst for the method |
| CN1378484A (en) * | 1999-07-16 | 2002-11-06 | 阿托菲纳公司 | Supported metal catalyst, preparation and applications for directly making hydrogen peroxide |
| US20050201925A1 (en) * | 2004-03-09 | 2005-09-15 | Bi Le-Khac | Process for making hydrogen peroxide |
| CN1880215A (en) * | 1999-07-16 | 2006-12-20 | 阿托菲纳公司 | Supported metal catalyst, preparation and applications for directly making hydrogen peroxide |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4127918A1 (en) * | 1991-03-05 | 1992-09-10 | Interox Int Sa | METHOD FOR PRODUCING HYDROGEN PEROXIDE |
| US6534440B2 (en) * | 2000-11-29 | 2003-03-18 | Council Of Scientific And Industrial Research | Process for the activation of a metallic palladium based catalyst useful for the direct oxidation of hydrogen to hydrogen peroxide |
| DE102004023766A1 (en) * | 2004-05-11 | 2005-12-01 | Degussa Ag | Process for the direct synthesis of hydrogen peroxide |
| US7288240B2 (en) * | 2004-06-25 | 2007-10-30 | Council Of Scientific And Industrial Research | Method for production of hydrogen peroxide with improved yield and selectivity by direct oxidation of hydrogen over palladium containing catalyst |
| KR20140053186A (en) * | 2011-07-15 | 2014-05-07 | 솔베이(소시에떼아노님) | Process to obtain hydrogen peroxide, and catalyst supports for the same process |
| US20140227166A1 (en) * | 2011-09-16 | 2014-08-14 | Solvay Sa | Catalyst for H202 synthesis and method for preparing such catalyst |
-
2017
- 2017-07-10 WO PCT/JP2017/025067 patent/WO2018016359A1/en active Application Filing
- 2017-07-10 JP JP2018528489A patent/JPWO2018016359A1/en active Pending
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038437A (en) * | 1988-05-13 | 1990-01-03 | 纳幕尔杜邦公司 | Use preferred H +And Br -Concentration is produced the method for hydrogen peroxide |
| JPH04360848A (en) * | 1991-06-05 | 1992-12-14 | Takasago Internatl Corp | Production of cyclic mono-or sesquiterpene ketone |
| CN1378484A (en) * | 1999-07-16 | 2002-11-06 | 阿托菲纳公司 | Supported metal catalyst, preparation and applications for directly making hydrogen peroxide |
| CN1880215A (en) * | 1999-07-16 | 2006-12-20 | 阿托菲纳公司 | Supported metal catalyst, preparation and applications for directly making hydrogen peroxide |
| CA2338104A1 (en) * | 2000-02-26 | 2001-08-26 | Degussa Ag | Method of producing hydrogen peroxide by direct synthesis and noble-metal catalyst for the method |
| US20050201925A1 (en) * | 2004-03-09 | 2005-09-15 | Bi Le-Khac | Process for making hydrogen peroxide |
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| WO2018016359A1 (en) | 2018-01-25 |
| TW201829060A (en) | 2018-08-16 |
| TWI740982B (en) | 2021-10-01 |
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