CN107335416A - A kind of catalyst nanoparticles dispersion liquid and preparation method and application - Google Patents
A kind of catalyst nanoparticles dispersion liquid and preparation method and application Download PDFInfo
- Publication number
- CN107335416A CN107335416A CN201710427768.0A CN201710427768A CN107335416A CN 107335416 A CN107335416 A CN 107335416A CN 201710427768 A CN201710427768 A CN 201710427768A CN 107335416 A CN107335416 A CN 107335416A
- Authority
- CN
- China
- Prior art keywords
- dispersion liquid
- catalyst nanoparticles
- metallic element
- cooled
- nanoparticles dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 106
- 239000006185 dispersion Substances 0.000 title claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 87
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000010992 reflux Methods 0.000 claims abstract description 49
- 238000013019 agitation Methods 0.000 claims abstract description 40
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000006228 supernatant Substances 0.000 claims abstract description 22
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 19
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005119 centrifugation Methods 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 229940049964 oleate Drugs 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000002912 waste gas Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000012074 organic phase Substances 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000008346 aqueous phase Substances 0.000 claims abstract description 3
- 238000009835 boiling Methods 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 26
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 26
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 26
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000005642 Oleic acid Substances 0.000 claims description 26
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000002440 industrial waste Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 238000012869 ethanol precipitation Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 46
- 238000001556 precipitation Methods 0.000 description 36
- 235000019441 ethanol Nutrition 0.000 description 21
- 238000000926 separation method Methods 0.000 description 20
- -1 oleyl amines Chemical class 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- IRXMQDYVKNENBF-KVVVOXFISA-N (z)-octadec-9-enoic acid;strontium Chemical compound [Sr].CCCCCCCC\C=C/CCCCCCCC(O)=O IRXMQDYVKNENBF-KVVVOXFISA-N 0.000 description 2
- LRTLEKVJKBCUQQ-KVVVOXFISA-N (z)-octadec-9-enoic acid;titanium Chemical compound [Ti].CCCCCCCC\C=C/CCCCCCCC(O)=O LRTLEKVJKBCUQQ-KVVVOXFISA-N 0.000 description 2
- CQXDDVVZHUFGSJ-KVVVOXFISA-N (z)-octadec-9-enoic acid;zirconium Chemical compound [Zr].CCCCCCCC\C=C/CCCCCCCC(O)=O CQXDDVVZHUFGSJ-KVVVOXFISA-N 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- PIVVWHQDANKXBE-KVVVOXFISA-N cerium;(z)-octadec-9-enoic acid Chemical compound [Ce].CCCCCCCC\C=C/CCCCCCCC(O)=O PIVVWHQDANKXBE-KVVVOXFISA-N 0.000 description 2
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(z)-octadec-9-enoate Chemical compound [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- CTTNXIBRLSQXOB-KVVVOXFISA-N lanthanum;(z)-octadec-9-enoic acid Chemical compound [La].CCCCCCCC\C=C/CCCCCCCC(O)=O CTTNXIBRLSQXOB-KVVVOXFISA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- XYXLRVFDLJOZJC-CVBJKYQLSA-L manganese(2+);(z)-octadec-9-enoate Chemical compound [Mn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O XYXLRVFDLJOZJC-CVBJKYQLSA-L 0.000 description 2
- AXLHVTKGDPVANO-UHFFFAOYSA-N methyl 2-amino-3-[(2-methylpropan-2-yl)oxycarbonylamino]propanoate Chemical compound COC(=O)C(N)CNC(=O)OC(C)(C)C AXLHVTKGDPVANO-UHFFFAOYSA-N 0.000 description 2
- MAQCMFOLVVSLLK-UHFFFAOYSA-N methyl 4-(bromomethyl)pyridine-2-carboxylate Chemical compound COC(=O)C1=CC(CBr)=CC=N1 MAQCMFOLVVSLLK-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- PXFAWKNRNHXITF-KVVVOXFISA-N nickel;(z)-octadec-9-enoic acid Chemical compound [Ni].CCCCCCCC\C=C/CCCCCCCC(O)=O PXFAWKNRNHXITF-KVVVOXFISA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 241000264877 Hippospongia communis Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/40—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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of metal or metal oxide nanoparticles dispersion liquid, preparation method to be:Take the nitrate and/or chloride of metallic element, described metallic element be aluminium, cerium, cobalt, copper, lanthanum, magnesium, manganese, nickel, strontium, titanium, zinc, zirconium, iron, platinum, one or both of palladium and more than, add enuatrol, add deionized water, ethanol and n-hexane, fully reacted at 60~80 DEG C of temperature, after being cooled to room temperature, separate aqueous phase and organic phase, it is washed with deionized and merges organic phase for several times, corresponding metal oleate is obtained after being evaporated;Metal oleate is mixed with high boiling organic solvent, under magnetic agitation, nitrogen atmosphere, 100~200 DEG C of 1~2h of condensing reflux, 200~300 DEG C of 0.5~1h of condensing reflux, room temperature is cooled to, adds ethanol precipitation, supernatant is cast out in centrifugation, add n-hexane to disperse, obtain corresponding catalyst nanoparticles dispersion liquid.Nanoparticle dispersion liquid of the present invention can be applied to the purification of waste gas, significant effect.
Description
Technical field
The present invention relates to technical field of air pollution control, more particularly to a kind of metal or metal oxide catalyst nanometer
Particle dispersion preparation method and the application in environmental catalysis field.
Background technology
As social development and process of industrialization are accelerated, fossil fuel is widely used, and be discharged into air poisonous has
Evil gas greatly increases, and atmosphere polluting problem was originally more serious.United Nations Environment Programme is in Second united nations environment conference
On point out that atmosphere pollution has turned into maximum environmental problem threatened human health in global range, prevention and control of air pollution situation is different
Chang Yanjun, it is extremely urgent to improve air quality.Catalysis technique provides the economic solution of uniqueness for the improvement of atmosphere pollution.
Such as:Motor vehicle tail-gas purifying, SOxWith NOxRemoving and VOCs catalysis oxidations, catalysis burning etc..Because these technologies can be relatively low
At a temperature of, by gaseous contaminant catalysis oxidation or nontoxic material is reduced into, conversion is thoroughly, secondary pollution is few, starts energy
Consume low, be one of effective means of current air contaminant treatment.
In actual waste gas pollution control and treatment at present to use support type integral catalyzer, preparation flow is substantially more:First in entirety
Applying coating on formula catalyst, catalyst by being coated or impregnated with load active component, is being made after activation, or will directly be made
Catalyst coated on carrier, then obtain catalyst after activated processing.Technology path is complex, obtained catalyst its
Surface active composition is easily reunited, not high in the firmness of carrier surface, and is limited by technique, and carrier need to possess certain size
Shape, therefore also have limitation when in use, it is impossible to flexible Application.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to provide a kind of metal or metal oxide nano grain
The preparation method of sub- dispersion liquid, the dispersion liquid containing active component is prepared using methods described, is then sprayed on carrier
Spill, loaded catalyst can easily be made.This method prepare simple, active component be not easy to reunite and with carrier binding ability
By force, it can be widely applied for the preparation of gaseous contaminant cleaning catalyst.Further, since nanoparticle dispersion liquid can arbitrarily spray
Apply, do not limited by base material, application potential is huge.
To use following technical scheme up to this purpose, the present invention:
A kind of catalyst nanoparticles dispersion liquid, the catalyst nanoparticles dispersion liquid are prepared as follows:
(1) take the nitrate and/or metallic element chloride of metallic element, described metallic element be aluminium, cerium, cobalt, copper,
One or both of lanthanum, magnesium, manganese, nickel, strontium, titanium, zinc, zirconium, iron, platinum, palladium and more than, add enuatrol, add volume ratio
2:3:5 deionized water, ethanol and n-hexane, fully react at 60~80 DEG C of temperature, after being cooled to room temperature, separation aqueous phase and have
Machine phase, is washed with deionized and merges organic phase for several times, and corresponding metal oleate is obtained after being evaporated;
(2) metal oleate made from step (1) is mixed with the organic solvent that boiling point is 250~350 DEG C, magnetic force stirs
Mix, under nitrogen atmosphere, 100~200 DEG C of 1~2h of condensing reflux, 200~300 DEG C of 0.5~1h of condensing reflux, be cooled to room temperature, add
Enter ethanol precipitation, supernatant is cast out in centrifugation, adds n-hexane and disperses, obtains corresponding catalyst nanoparticles dispersion liquid.
Further, the nitrate and/or metallic element of the sodium ion quantity of electric charge of enuatrol of the present invention and metallic element
The metal ion total charge dosage of chloride is equal.
Further, the volumetric usage of deionized water described in step (1) of the present invention is with the nitrate and/or gold of metallic element
The amount for belonging to the total material of element chloride is calculated as 1mL/mmol.
Further, the volumetric usage of ethanol described in step (1) of the present invention is with the nitrate of metallic element and/or metal member
The amount of the total material of plain chloride is calculated as 1.5mL/mmol.
Further, the volumetric usage of n-hexane described in step (1) of the present invention is with the nitrate and/or metal of metallic element
The amount of the total material of element chloride is calculated as 2.5mL/mmol.
Further, temperature is preferably 70 DEG C described in step (1) of the present invention.
Further, organic solvent described in step (2) of the present invention is the ratio between volume 4:1 oleyl amine and oleic acid.
Further, the volumetric usage of organic solvent described in step (2) of the present invention is with the gauge of the material of metal oleate
For 5~10mL/mmol.
Further, centrifuged described in step (2) of the present invention under preferred 6000rpm and separate 10min.
Further, the present invention provides the purification that a kind of described catalyst nanoparticles dispersion liquid is applied to waste gas.
Further, waste gas of the present invention is industrial waste gas, motor-vehicle tail-gas or the interior based on hydrocarbon
Formaldehyde.
Active component of the present invention refers to obtained various metals or metal oxide.
The application of metal or metal oxide nanoparticles dispersion liquid of the present invention, specific embodiment are as follows:
(1) obtained active nanoparticles dispersion liquid is evaporated, is swept by roasting or flame gun spray, obtain respective metal oxygen
Compound fine catalyst is used for the purification of waste gas.
(2) obtained nanoparticle dispersion liquid is spilt and is coated in pelleted substrate (such as Al2O3) or ceramic honey comb matrix (such as violet
Green stone) on, drying, swept by roasting or flame gun spray, the loaded catalyst for obtaining loading corresponding active component is used for waste gas
Purification.
(3) nanoparticle dispersion liquid made from is not limited only to be sprayed on conventional carrier, and any surface can all be carried out
Sprinkling, can flexibly set catalyst, make catalyst ubiquitous.
Beneficial effect of the present invention is mainly reflected in:(1) element of active component of the present invention can be transition metal, rare earth metal
With noble metal etc., it is applied widely;(2) active component is preserved in the form of nanoparticle dispersion liquid, can pass through the sprinkling of simplicity
Load on carrier, it is simple to operate;(3) corresponding nanoparticle dispersion liquid can be prepared by method provided by the invention as needed
For all kinds of environmental catalysis;(4) have by purification of the inventive method especially to degradation of indoor air VOCs sizable
Application potential.
Brief description of the drawings
Fig. 1~12 are each metal dispersion sample and TEM, XRD made from embodiment 1~12.
Figure 13 is different carriers loaded Cu Ce catalyst activity figures in embodiment 15.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1
Weigh 1.5g Al (NO3)3·9H2O, 3.648g enuatrols, 10mL n-hexanes, 6mL ethanol, 4mL deionizations are added
Water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, spend
Ion water washing 3 times, discards lower floor's liquid, and supernatant liquid obtains aluminum oleate after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in aluminum oleate obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 2
Weigh 1.736g Ce (NO3)3·6H2O, 3.648g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL go from
Sub- water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, uses
Deionized water is washed 3 times, discards lower floor's liquid, supernatant liquid obtains oleic acid cerium after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in oleic acid cerium obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 3
Weigh 1.164g Co (NO3)2·6H2O, 2.432g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL go from
Sub- water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, uses
Deionized water is washed 3 times, discards lower floor's liquid, supernatant liquid obtains cobalt oleate after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in cobalt oleate obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 4
Weigh 0.968g Cu (NO3)2·3H2O, 2.432g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL go from
Sub- water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, uses
Deionized water is washed 3 times, discards lower floor's liquid, supernatant liquid obtains copper oleate after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in copper oleate obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 5
Weigh 1.732g La (NO3)3·6H2O, 3.648g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL go from
Sub- water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, uses
Deionized water is washed 3 times, discards lower floor's liquid, supernatant liquid obtains oleic acid lanthanum after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in oleic acid lanthanum obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 6
Weigh 1.042g Mg (NO3)2·6H2O, 2.432g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL go from
Sub- water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, uses
Deionized water is washed 3 times, discards lower floor's liquid, supernatant liquid obtains magnesium oleate after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in magnesium oleate obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 7
Pipette 0.93mL 50wt%Mn (NO3)2, 2.432g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL go from
Sub- water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, uses
Deionized water is washed 3 times, discards lower floor's liquid, supernatant liquid obtains manganese oleate after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in manganese oleate obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 8
Weigh 1.164g Ni (NO3)2·6H2O, 2.432g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL go from
Sub- water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, uses
Deionized water is washed 3 times, discards lower floor's liquid, supernatant liquid obtains oleic acid nickel after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in oleic acid nickel obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 9
Weigh 0.848g Sr (NO3)2, 2.432g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL deionized waters.
Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, use deionization
Water washing 3 times, discards lower floor's liquid, and supernatant liquid obtains oleic acid strontium after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in oleic acid strontium obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 10
Pipette 1.5mL TiCl3Solution, 3.648g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL deionized waters.
Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, and moves into separatory funnel liquid separation, spend from
Sub- water washing 3 times, discards lower floor's liquid, supernatant liquid obtains oleic acid titanium after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in oleic acid titanium obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 11
Weigh 0.544g ZnCl2, 2.432g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL deionized waters.70
Under the conditions of DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, use deionized water
Washing 3 times, discards lower floor's liquid, supernatant liquid obtains zinc oleate after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in zinc oleate obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 12
Weigh 1.716g Zr (NO3)4·5H2O, 4.864g enuatrols, add 10mL n-hexanes, 6mL ethanol, 4mL go from
Sub- water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, uses
Deionized water is washed 3 times, discards lower floor's liquid, supernatant liquid obtains oleic acid zirconium after being evaporated.
20mL oleyl amines, 5mL oleic acid are added in oleic acid zirconium obtained above.Under magnetic agitation, nitrogen atmosphere, 200 DEG C cold
Solidifying backflow 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 13
Weigh 0.54g FeCl3·6H2O, 0.47mL 50wt%Mn (NO3)2, 3.04g enuatrols, add 10mL just oneself
Alkane, 6mL ethanol, 4mL deionized waters.Under the conditions of 80 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating,
Separatory funnel liquid separation is moved into, is washed with deionized 3 times, discards lower floor's liquid, supernatant liquid obtains Fe-Mn oleic acid after being evaporated
Salt.
20mL oleyl amines, 5mL oleic acid are added in Fe-Mn oleates obtained above.Under magnetic agitation, nitrogen atmosphere, 200
DEG C condensing reflux 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes,
Centrifuge (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, is formed corresponding nano-particle and is disperseed
Liquid.
Embodiment 14
Weigh 0.484g Cu (NO3)2·3H2O、0.868g Ce(NO3)3·6H2O and 3.04g enuatrols, adding 10mL just
Hexane, 6mL ethanol, 4mL deionized waters.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room after terminating
Temperature, separatory funnel liquid separation is moved into, is washed with deionized 3 times, discard lower floor's liquid, supernatant liquid obtains Cu-Ce oil after being evaporated
Hydrochlorate.
20mL oleyl amines, 5mL oleic acid are added in Cu-Ce oleates obtained above.Under magnetic agitation, nitrogen atmosphere, 200
DEG C condensing reflux 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes,
Centrifuge (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, is formed corresponding nano-particle and is disperseed
Liquid.
Embodiment 15
Dispersion liquid made from embodiment 14 is sprayed at carrier surface, the present embodiment from cordierite (Cordierite),
Brick (Brick) and iron sheet (Iron sheet) are used as carrier, are calcined 3h at 400 DEG C, obtain CuCe loaded catalysts, use
In toluene catalytic combustion performance test:Toluene generator is placed in mixture of ice and water (0 DEG C), input concentration 2000ppm, reaction
Air speed is 370000mLh-1·gcat -1(on the basis of active component), catalyst combustion reaction tail gas divide online through gas-chromatography
Analysis, monitoring outlet toluene concentration, and conversion ratio is calculated, as shown in figure 13.
Embodiment 16
Weigh 0.177g PdCl2, 0.608g enuatrols, add 2.5mL n-hexanes, 1.5mL ethanol, 1mL deionized waters.
Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, and moves into separatory funnel liquid separation, spend from
Sub- water washing 3 times, discards lower floor's liquid, supernatant liquid obtains oleic acid palladium after being evaporated.
4mL oleyl amines, 1mL oleic acid are added in oleic acid palladium obtained above.Under magnetic agitation, nitrogen atmosphere, 100 DEG C of condensations
Flow back 1h, 200 DEG C of condensing reflux 0.5h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 17
Weigh 0.177g PdCl2, 0.608g enuatrols, add 2.5mL n-hexanes, 1.5mL ethanol, 1mL deionized waters.
Under the conditions of 60 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, and moves into separatory funnel liquid separation, spend from
Sub- water washing 3 times, discards lower floor's liquid, supernatant liquid obtains oleic acid palladium after being evaporated.
8mL oleyl amines, 2mL oleic acid are added in oleic acid palladium obtained above.Under magnetic agitation, nitrogen atmosphere, 100 DEG C of condensations
Flow back 1h, 200 DEG C of condensing reflux 0.5h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes, centrifugation
Separate (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms corresponding nanoparticle dispersion liquid.
Embodiment 18
Weigh 0.337g PtCl4, 1.216g enuatrols, add 2.5mL n-hexanes, 1.5mL ethanol, 1mL deionized waters.
Under the conditions of 60 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, and moves into separatory funnel liquid separation, spend from
Sub- water washing 3 times, discards lower floor's liquid, supernatant liquid obtains platinum oleate after being evaporated.
5mL oleyl amines, 1.25mL oleic acid are added in platinum oleate obtained above.Under magnetic agitation, nitrogen atmosphere, 100 DEG C
Condensing reflux 1h, 200 DEG C of condensing reflux 0.5h.Reaction is cooled to room temperature after terminating, add the absolute ethyl alcohol precipitation of 3 times of volumes,
Centrifuge (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, is formed corresponding nano-particle and is disperseed
Liquid.
Embodiment 19
A certain amount of cerous nitrate is taken, zirconium nitrate, platinum chloride and enuatrol, a certain proportion of n-hexane, ethanol is added and goes
Ionized water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation,
It is washed with deionized 3 times, discards lower floor's liquid, supernatant liquid obtains corresponding oleate precursor after is evaporated.
A certain proportion of oleyl amine, oleic acid are added in oleate precursor obtained above.Under magnetic agitation, nitrogen atmosphere,
200 DEG C of condensing refluxes 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, the absolute ethyl alcohol for adding 3 times of volumes sinks
Form sediment, centrifuge (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms Pt/CeZr nano-particles
Dispersion liquid.Obtained dispersion liquid can be used for spraying in motor vehicle exhaustion system, strengthen catalysis oxidation ability.In experiment, with Pt/
CeZr fine catalysts are research object, steel cylinder gas simulation diesel engine vent gas composition, concrete component is CO 1 ‰, NO 0.5 ‰,
C3H6 0.5‰、O210%th, N2For Balance Air, air speed 17000mLh-1·gcat -1, catalyst combustion reaction tail gas is through gas phase color
On-line analysis, monitoring outlet propylene and carbonomonoxide concentration are composed, and calculates conversion ratio.As a result show, to propylene and one at 300 DEG C
Charcoal percent conversion is aoxidized up to more than 95%.
Embodiment 20
A certain amount of titanium tetrachloride, platinum chloride and enuatrol are taken, adds a certain proportion of n-hexane, ethanol and deionization
Water.Under the conditions of 70 DEG C, magnetic agitation condensing reflux 4h.Reaction is cooled to room temperature after terminating, move into separatory funnel liquid separation, spend
Ion water washing 3 times, discards lower floor's liquid, and supernatant liquid obtains corresponding oleate precursor after being evaporated.
A certain proportion of oleyl amine, oleic acid are added in oleate precursor obtained above.Under magnetic agitation, nitrogen atmosphere,
200 DEG C of condensing refluxes 2h, 300 DEG C of condensing reflux 1h.Reaction is cooled to room temperature after terminating, the absolute ethyl alcohol for adding 3 times of volumes sinks
Form sediment, centrifuge (6000rpm, 10min) 3 times, the precipitation of gained is most disperseed through n-hexane afterwards, forms Pt/TiO2Nano-particle
Dispersion liquid.Obtained dispersion liquid can be used on some objects indoors spraying, with formaldehyde room temperature catalytic oxidation ability.
In experiment, with Pt/TiO2Fine catalyst is research object, and 37% formalin, which is placed in mixture of ice and water (0 DEG C), to be carried out
Bubbling, input concentration 1.5ppm, reaction velocity 60000mLh-1·gcat-1, catalytic oxidation tail gas phenol reagent
Spectrophotometry, calculate armatine aldehyde concentration and conversion ratio.As a result show, at 25 DEG C, formaldehyde conversion is up to 80%
More than.
Claims (8)
1. a kind of catalyst nanoparticles dispersion liquid, it is characterised in that the catalyst nanoparticles dispersion liquid is made by the following method
It is standby:
(1) take the nitrate and/or metallic element chloride of metallic element, described metallic element be aluminium, cerium, cobalt, copper, lanthanum,
One or both of magnesium, manganese, nickel, strontium, titanium, zinc, zirconium, iron, platinum, palladium and more than, add enuatrol, add volume ratio 2:3:
5 deionized water, ethanol and n-hexane, fully react at 60~80 DEG C of temperature, after being cooled to room temperature, separate aqueous phase and organic
Phase, it is washed with deionized and merges organic phase for several times, corresponding metal oleate is obtained after being evaporated;
(2) metal oleate made from step (1) is mixed with the organic solvent that boiling point is 250~350 DEG C, magnetic agitation, nitrogen
Under gas atmosphere, 100~200 DEG C of condensing refluxes 1~2h, 200~300 DEG C of 0.5~1h of condensing reflux, room temperature is cooled to, adds second
Alcohol precipitates, and supernatant is cast out in centrifugation, adds n-hexane and disperses, obtains corresponding catalyst nanoparticles dispersion liquid.
2. catalyst nanoparticles dispersion liquid as claimed in claim 1, it is characterised in that:The sodium ion electric charge of the enuatrol
Amount is equal with the nitrate of metallic element and/or the metal ion total charge dosage of metallic element chloride.
3. catalyst nanoparticles dispersion liquid as claimed in claim 1, it is characterised in that:Deionized water described in step (1)
Volumetric usage 1mL/mmol is calculated as with the amount of the nitrate of metallic element and/or the total material of metallic element chloride.
4. catalyst nanoparticles dispersion liquid as claimed in claim 1, it is characterised in that:Temperature described in step (1) is 70
℃。
5. catalyst nanoparticles dispersion liquid as claimed in claim 1, it is characterised in that:Organic solvent described in step (2)
For the ratio between volume 4:1 oleyl amine and oleic acid.
6. catalyst nanoparticles dispersion liquid as claimed in claim 1, it is characterised in that:Organic solvent described in step (2)
Volumetric usage 5~10mL/mmol is calculated as with the amount of the material of metal oleate.
7. catalyst nanoparticles dispersion liquid as claimed in claim 1 is applied to the purification of waste gas.
8. application as claimed in claim 7, it is characterised in that:The waste gas for based on hydrocarbon industrial waste gas,
Motor-vehicle tail-gas or indoor formaldehyde.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710427768.0A CN107335416A (en) | 2017-06-08 | 2017-06-08 | A kind of catalyst nanoparticles dispersion liquid and preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710427768.0A CN107335416A (en) | 2017-06-08 | 2017-06-08 | A kind of catalyst nanoparticles dispersion liquid and preparation method and application |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107335416A true CN107335416A (en) | 2017-11-10 |
Family
ID=60220567
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710427768.0A Pending CN107335416A (en) | 2017-06-08 | 2017-06-08 | A kind of catalyst nanoparticles dispersion liquid and preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107335416A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108404916A (en) * | 2018-05-04 | 2018-08-17 | 河南科技学院 | A kind of preparation method of metal Co catalysts and its application in Butadiene hydrogenation reaction |
CN108772067A (en) * | 2018-06-05 | 2018-11-09 | 天津大学 | The preparation method of the monoatomic ACF catalyst of the double transition metal of load of room temperature degradation VOCs |
CN109985661A (en) * | 2019-04-29 | 2019-07-09 | 无锡威孚环保催化剂有限公司 | Catalyst and preparation method based on purification of volatile organic pollutant |
CN114644845A (en) * | 2022-04-08 | 2022-06-21 | 中国科学院过程工程研究所 | Heat-conducting catalyst coating and preparation method and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101015806A (en) * | 2007-02-15 | 2007-08-15 | 浙江工业大学 | Metal mesh type combustion catalyst and its preparing process and application |
CN104261488A (en) * | 2014-09-28 | 2015-01-07 | 济南大学 | Preparation method of nanometer Fe3O4 octahedral structure |
CN104466169A (en) * | 2014-12-23 | 2015-03-25 | 中南大学 | Method for preparing ferrum electrode material of ferro-nickel rechargeable secondary battery |
CN105668606A (en) * | 2016-03-11 | 2016-06-15 | 九江学院 | Preparing method for square nanometer flake cerium oxide |
CN106623973A (en) * | 2016-12-19 | 2017-05-10 | 北京大学 | Controllable synthesis method for nickel platinum alloy nano-particles |
CN106635021A (en) * | 2016-12-19 | 2017-05-10 | 厦门大学 | Preparation method of rare-earth doped nanoparticles |
-
2017
- 2017-06-08 CN CN201710427768.0A patent/CN107335416A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101015806A (en) * | 2007-02-15 | 2007-08-15 | 浙江工业大学 | Metal mesh type combustion catalyst and its preparing process and application |
CN104261488A (en) * | 2014-09-28 | 2015-01-07 | 济南大学 | Preparation method of nanometer Fe3O4 octahedral structure |
CN104466169A (en) * | 2014-12-23 | 2015-03-25 | 中南大学 | Method for preparing ferrum electrode material of ferro-nickel rechargeable secondary battery |
CN105668606A (en) * | 2016-03-11 | 2016-06-15 | 九江学院 | Preparing method for square nanometer flake cerium oxide |
CN106623973A (en) * | 2016-12-19 | 2017-05-10 | 北京大学 | Controllable synthesis method for nickel platinum alloy nano-particles |
CN106635021A (en) * | 2016-12-19 | 2017-05-10 | 厦门大学 | Preparation method of rare-earth doped nanoparticles |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108404916A (en) * | 2018-05-04 | 2018-08-17 | 河南科技学院 | A kind of preparation method of metal Co catalysts and its application in Butadiene hydrogenation reaction |
CN108404916B (en) * | 2018-05-04 | 2020-09-11 | 河南科技学院 | Preparation method of metal cobalt catalyst and application of metal cobalt catalyst in catalyzing butadiene hydrogenation reaction |
CN108772067A (en) * | 2018-06-05 | 2018-11-09 | 天津大学 | The preparation method of the monoatomic ACF catalyst of the double transition metal of load of room temperature degradation VOCs |
CN109985661A (en) * | 2019-04-29 | 2019-07-09 | 无锡威孚环保催化剂有限公司 | Catalyst and preparation method based on purification of volatile organic pollutant |
CN114644845A (en) * | 2022-04-08 | 2022-06-21 | 中国科学院过程工程研究所 | Heat-conducting catalyst coating and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107335416A (en) | A kind of catalyst nanoparticles dispersion liquid and preparation method and application | |
US8574520B2 (en) | Metal oxide support material containing nanoscaled iron platinum group metal | |
CN101400441B (en) | Catalyst for exhaust-gas purification and process for producing the same | |
JP4547935B2 (en) | Exhaust gas purification catalyst, exhaust gas purification catalyst, and catalyst manufacturing method | |
CN108671908A (en) | Method for the deposited metal in support oxide | |
WO2016123523A1 (en) | Rhodium-containing catalysts for automotive emissions treatment | |
CN106111145B (en) | Imperfect structure copper oxide and cerium oxide symbiotic co-existence catalyst and preparation method thereof | |
CN105148907A (en) | 1, 2-dichloroethane selective hydrodechlorination reaction catalyst and preparation method and application thereof | |
US20140194280A1 (en) | Nox purification catalyst | |
CN108452798A (en) | A kind of high temperature resistant sintering loaded noble metal catalyst and preparation method thereof for catalyzing carbon monoxide oxidation | |
CN103534024B (en) | NO xcleaning catalyst and preparation method thereof | |
JP2006320797A (en) | Catalyst and its manufacturing method | |
US9079167B2 (en) | NOx purification catalyst | |
CN113976176B (en) | Platinum-based catalyst with double active sites and preparation method and application thereof | |
WO2006095392A1 (en) | Process for producing catalyst for discharge gas treatment | |
JP6359678B2 (en) | Composite particle dispersion and method for producing the same | |
JP6359679B2 (en) | Composite particle dispersion and method for producing the same | |
JP2008238106A (en) | Catalyst and method for treating exhaust gas | |
JP6107683B2 (en) | Method for producing exhaust gas purification catalyst | |
EP2680952B1 (en) | Nox purification catalyst | |
JP2005185959A (en) | Catalyst for exhaust emission purification | |
WO2023063353A1 (en) | Catalyst | |
Evangelisti et al. | Solvated metal atoms in the preparation of supported gold catalysts | |
Özarslan | Preparation and NOx Reduction Performance of Ag-Ni-TiO2/Cordierite Catalyst for HC-SCR System | |
EP2673070B1 (en) | Nox purification catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171110 |