CN108927162A - 铜基湿式氧化催化剂的制备方法 - Google Patents
铜基湿式氧化催化剂的制备方法 Download PDFInfo
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- CN108927162A CN108927162A CN201710366541.XA CN201710366541A CN108927162A CN 108927162 A CN108927162 A CN 108927162A CN 201710366541 A CN201710366541 A CN 201710366541A CN 108927162 A CN108927162 A CN 108927162A
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- copper
- preparation
- wet oxidizing
- oxidizing catalyst
- solution
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 40
- 239000010949 copper Substances 0.000 title claims abstract description 40
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 230000001376 precipitating effect Effects 0.000 claims abstract description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 239000012692 Fe precursor Substances 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 9
- 206010001497 Agitation Diseases 0.000 abstract 1
- 238000013019 agitation Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 22
- 229910052593 corundum Inorganic materials 0.000 description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 239000002002 slurry Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- 230000010355 oscillation Effects 0.000 description 10
- 229910020203 CeO Inorganic materials 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 238000009279 wet oxidation reaction Methods 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 239000000908 ammonium hydroxide Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 244000073231 Larrea tridentata Species 0.000 description 1
- 235000006173 Larrea tridentata Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960002126 creosote Drugs 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003292 glue Substances 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
- 239000008187 granular material Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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Abstract
本发明公开了一种铜基湿式氧化催化剂及其制备方法,包括(1)将铝源前驱体溶解形成溶液;(2)将铜源前驱体溶解形成溶液,并将(1)和(2)混合;(3)对步骤(2)所得溶液混合均匀后,调节pH值形成沉淀,过滤,洗涤;(4)在步骤(3)所得滤饼中加入去离子水,调成浆状,加入铈源前驱体溶液,均匀混合后,直接进行干燥、焙烧,形成粉状物;(5)将步骤(4)的粉状物与铁源前驱体溶液混合成浆状,搅拌后,加硅溶胶、造孔剂,二次搅拌后,密封静置、干燥、焙烧,形成湿式氧化催化剂。本发明制备的湿式氧化催化剂用于高浓度有机废水,具有成本低、性能稳定等特点。
Description
技术领域
本发明涉及一种复合金属氧化物催化剂的制备方法,具体是一种用于湿式氧化的铜基催化剂的制备方法。
背景技术
湿式(空气)氧化(wet air oxidation,WAO)处理高浓度难降解有机废水,通常需要较高的温度和压力(200~3l5℃,2~21MPa)以及较长的停留时间,其反应条件非常苛刻。催化湿式氧化catalytic wetair oxidation,CWAO)在保持处理效果的条件下,可降低反应温度和压力,极大地推动湿式氧化的发展和应用。因此,研制具有较高活性和稳定性并适用于CWAO的催化剂,成为目前研究的重点和难点。炼油或乙烯废碱液(碱渣)中除含有不同浓度的游离碱(NaOH),还含有大量高浓的Na2S、有机酸性物质(以钠盐形式存在,如杂酚、环烷酸、硫醇、硫酚等)、硫醚以及噻吩等有机硫化物,呈恶臭、有毒,COD含量高达10 000~150000mg/L,在催化湿式氧化过程中易发生催化剂中毒、金属活性成分流失以及COD去除效率低等问题,成为研究的难点。
CN1358567公开“一种用于催化湿式氧化处理工业废水的铜基催化剂及其制备方法”,一种用于催化湿式氧化处理工业废水的铜基催化剂的制备及应用。催化剂的主要成分为铜、锌、镍、镁、铝、铬、铁和一部分稀土金属的氧化物,其中以氧化物的含量来计算:CuO为20~55%;ZnO、NiO或MgO为20~55%;Cr2O3、Al2O3或Fe2O3为10~40%;稀土金属氧化物为0~10%。该催化剂由含有各种金属的盐共沉淀得到类水滑石结构的催化剂前驱体,并焙烧所得。该催化剂经过一次共沉淀、焙烧而成,能有效处理含酚、磺基水杨酸、H-酸和表面活性剂等有毒难降解的工业有机废水,铜流失量较低,但难以适应处理含有多种有毒、有害物质废水的需要,尤其是炼油或乙烯废碱液的处理中COD去除效率低。
CN1669643公开了一种稀土复合氧化物催化剂,其为固体粉末状,组分为ZrO2和CeO的复合氧化物,Zr和Ce的摩尔比为1∶1~1∶11。本发明还公开了所述催化剂的制备方法:将锆盐和铈盐溶液混合,采用一步沉淀法,一次干燥、焙烧得到催化剂。本发明所制备的催化剂仅对于含高浓度难降解的小分子有机酸废水有良好的活性和较高的稳定性,难以适应处理含有多种有毒、有害物质废水的需要,尤其是炼油或乙烯废碱液的处理。
CN104667934公开“一种催化湿式氧化催化剂的制备方法”,采用过度和稀土金属为活性金属组分,浸渍于载体上,采用一次浸渍和一次焙烧后,实现催化剂的制备。
综上所述,湿式氧化催化剂的制备均采用一次沉淀,一次焙烧而成,在催化湿式氧化过程中对废水中的COD、有机物有一定的去除作用,但是,目前的湿式氧化催化剂对废碱液处理效果过程中,催化剂易中毒、COD去除效率低、活性组分铜易于流失,影响催化剂的性能。
发明内容
本发明提供一种改进的铜基湿式氧化催化剂制备方法,使制备的催化剂既可以抵抗催化剂在多种污染物共存体系中的中毒、失活,有效成分易流失的问题,又可以提高催化剂强度,提高催化剂的稳定性,延长使用周期。
本发明一种铜基湿式氧化催化剂的制备方法包括如下步骤:
(1)将铝源前驱体溶解形成溶液;
(2)将铜源前驱体溶解,并将其与步骤(1)的溶液混合;
(3)对步骤(2)所得溶液均匀混合后,调节pH值形成沉淀,过滤,洗涤;
(4)在步骤(3)所得滤饼中加入去离子水,调成浆状,加入铈源前驱体均匀混合后,直接进行干燥、焙烧,形成粉状物;
(5)将步骤(4)的粉状物与铁源前驱体溶液混合成浆状,搅拌后,加造孔剂,硅溶胶二次混合后,密封静置、干燥、焙烧,形成湿式氧化催化剂。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(1)所述铝源前驱体为可溶性的铝盐和/或偏铝酸盐,优选为硝酸铝,对铝源前驱体的溶解,形成溶液以Al2O3计,含量优选为15~40g/L。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(2)所述铜源前驱体为可溶性的铜盐,优选为硝酸铜,对铜源前驱体的溶解,形成溶液以CuO计,含量优选为15~40g/L。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(3)和步骤(4)中混合时间均优选为0.5~3h,所述步骤(5)中搅拌时间均优选为10~60min,步骤(5)中密封静置时间优选为8~30h。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(3)pH值的调节可采用氨水、氢氧化钠等酸碱调节剂,优选氨水,pH范围4~13,优选8~11。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(4)所述铈源前驱体为可溶性的铈盐,优选为硝酸铈,所述步骤(4)形成物料以CeO计,含量优选为15~40g/L。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(5)所述铁源前驱体为可溶性的铁盐,优选为硝酸铁,所述步骤(5)形成物料以Fe2O3计,含量优选为15~40g/L。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(5)所述造孔剂可以是柠檬酸、尿素、三氯乙酸、活性炭、田菁粉一种或多种,优选柠檬酸和田菁粉复合药剂,造孔剂与Al2O3质量比优选比例为0.5~1.5:100。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(5)所述,以SiO2计硅溶胶与Al2O3质量比为3~5:100。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(4)和步骤(5)中焙烧温度为400~850℃,均优选为500~650℃,焙烧时间不少于1小时,均优选为2~7h。
本发明一种铜基湿式氧化催化剂的制备方法,其中步骤(3)、(4)及(5)中所述的混合方法包括各种机械搅拌、流体混合和超声波混合,其中优选超声波法。
本发明方法制备的湿式氧化催化剂,以重量百分比计,其中含氧化铝50~90%,含氧化铜2~10%,含氧化铈5~20%,含氧化铁为1~15%,硅溶胶(以SiO2计)2~5%;比表面为60~160m2/g,孔容0.30~0.70cm3/g。
本发明的铜基湿式氧化催化剂制备方法,将铝、铜、铈粉体物料经过一次焙烧后,又在其表面覆盖一层氧化铁,同时加入了造孔剂、硅溶胶后再次焙烧,可以减少催化剂在湿式氧化过程中铜的流失,使催化剂颗粒表面具有更多氧化铁附着,同时还拥有丰富的空间网络状纳米级微孔和较高的压碎强度,可以保证高的催化剂性能。硅溶胶在焙烧过程中,胶体粒子以化学键(Si-O-Si)相结合,形成稳定的空间网络结构,与氧化铝牢固结合,产生更丰富的孔径分布,更高的机械强度,并在氧化铝颗粒表面形成纳米包覆的微复合结构,减少催化剂在湿式氧化过程中铜的流失,保证高的催化剂性能。本发明方法工艺简单,且无贵金属成分,成本更低,具有广泛的应用前景。
本发明方法制备的催化剂,可处理高含量的含酚类、硫化物有机废水,COD含量范围10000~150000之间的废水可直接进行处理,在压力为1.0~5.0MPa,反应为温度190~260℃、反应时间0.5~4.0h,以过量空气或富养空气为氧化介质,经过催化湿式氧化处理后,硫化物的转化率可达99.9%以上,酚类转化率可达90%以上,对COD的去除率可达85.0%以上,废水处理后BOD/COD的比值由0.1以下,提到0.40以上,有利于废水的进一步达标处理。
具体实施方式
以下实施例是对本发明的具体说明,实施例和对比例所述的“%”指质量百分含量。
实施例1
将含以Al2O3计70g的氯化铝溶解,形成含Al2O3为35g/L混合溶液,加入含以CuO计5g的硝酸铜溶液,超声波振荡2h后逐步加入氨水调节pH值至9,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计7g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,550℃下焙烧2h;焙烧后粉体再与以Fe2O3计10g的硝酸铁溶液制成含水30%的浆料,搅拌后加入1g柠檬酸,以SiO2计2.4g硅溶胶,搅拌40min、密封静置24h、烘干、650℃焙烧7h后得到湿式氧化催化剂1。
实施例2
将含以Al2O3计70g的氯化铝溶解,形成含Al2O3为35g/L混合溶液,加入含以CuO计2g的硝酸铜溶液,超声波振荡2h后逐步加入氨水调节pH值至8.5,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计10g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,600℃下焙烧3h;焙烧后粉体再与以Fe2O3计5g的硝酸铁溶液制成含水30%的浆料,搅拌后加入1g柠檬酸,以SiO2计3g硅溶胶搅拌40min、密封静置30h、烘干、600℃焙烧5h后得到湿式氧化催化剂2。
实施例3
将含以Al2O3计70g的氯化铝溶解,形成含Al2O3为30g/L混合溶液,加入含以CuO计7g的硝酸铜溶液,机械搅拌2h后逐步加入氨水调节pH值至9.0,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计5g的硝酸铈溶液,搅拌的同时超声波振荡3h,直接干燥后,550℃下焙烧5h;焙烧后粉体再与以硝酸铁7g的硝酸铁溶液制成含水30%的浆料,搅拌后加入1.5g柠檬酸,以SiO2计3.5g硅溶胶,搅拌60min、密封静置10h、烘干、600℃焙烧6h后得到湿式氧化催化剂3。
实施例4
将含以Al2O3计70g的氯化铝溶解,形成含Al2O3为30g/L混合溶液,加入含以CuO计5g的硝酸铜溶液,超声波振荡2h后逐步加入氨水调节pH值至9.5,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计5g的硝酸铈溶液,搅拌的同时超声波振荡3h,直接干燥后,550℃下焙烧5h;焙烧后粉体再与以Fe2O3计5g的硝酸铁溶液制成含水30%的浆料,搅拌后加入1.0g三氯乙酸,以SiO2计3.5g硅溶胶,搅拌40min、密封静置10h、烘干、600℃焙烧5h后得到湿式氧化催化剂4。
实施例5
将含以Al2O3计70g的氯化铝溶解,形成含Al2O3为35g/L混合溶液,加入含以CuO计5g的硝酸铜溶液,超声波振荡2h后逐步加入氨水调节pH值至8.5,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计7g的硝酸铈溶液,搅拌的同时超声波振荡3h,直接干燥后,550℃下焙烧5h;焙烧后粉体再与以Fe2O3计7.5g的硝酸铁溶液制成含水30%的浆料,搅拌后加入1.0g三氯乙酸,以SiO2计3g硅溶胶,搅拌40min、密封静置10h、烘干、600℃焙烧5h后得到湿式氧化催化剂5。
对比例6
将含以Al2O3计76g的氯化铝溶解,形成含Al2O3为30g/L混合溶液,加入含以CuO计5g的硝酸铜溶液,机械搅拌2h后逐步加入氨水调节pH值至9.5,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计7g的硝酸铈溶液,搅拌的同时超声波振荡3h,直接干燥后,500℃下焙烧4h;焙烧后粉体再与以NiO计7g的硝酸镍溶液制成含水30%的浆料,搅拌后加入1.0g柠檬酸,搅拌40min、密封静置10h、烘干、500℃焙烧5h后得到湿式氧化催化剂6。
对比例7
将含以Al2O3计76g的氯化铝溶解,形成含Al2O3为30g/L混合溶液,加入含以CuO计5g的硝酸铜溶液,以CeO计7g的硝酸铈溶液,以NiO计7g的硝酸镍溶液,机械搅拌2h后逐步加入氨水调节pH值至9.5,沉淀完全后,过滤、洗涤;密封静置10h、烘干、500℃焙烧5h后得到湿式氧化催化剂7。
各催化剂样品的物理性质如表1所示:
表1催化剂样品物性数据
评价结果
将上述1~7催化剂颗粒5ml,装填在微型连续流动固定床反应器中,通入含废碱渣,组成COD为85000mg/L、硫化物含量7500mg/L、酚类含量为12000mg/L,加入压缩空气,控制反应压力为3.5Mpa,温度230℃,反应时间2.5h的条件下进行评价试验。
通过评价试验,各催化剂的转化率数据分别见表2、表3:
表2实施例催化剂评价结果
从表2可以看出:应用本发明的制备方法制备的催化剂,处理炼油废碱渣或含酚有机废水,硫化物去除率可达99.9%,COD去除率可达85%以上,酚类去除率可达90%以上。
当反应温度230℃,反应时间为2小时,催化剂重复使用6次后,检测催化剂处理效果及反应液中铜离子的浓度,结果见表3。由实验结果可以看到,本发明的催化剂处理废碱液后,催化剂1~6对比催化剂7铜离子流失情况得到较好控制,COD去除效果更高,且活性保持稳定。
表3催化剂连续运行评价结果
Claims (9)
1.一种铜基湿式氧化催化剂的制备方法,其特征在于,包括如下步骤:
(1)将铝源前驱体溶解形成溶液;
(2)将铜源前驱体溶解,并将其与步骤(1)的溶液混合;
(3)对步骤(2)所得溶液混合后调节pH值形成沉淀,过滤,洗涤;
(4)在步骤(3)所得滤饼中加入去离子水,加入铈源前驱体混合后进行干燥、焙烧,形成粉状物;
(5)将步骤(4)的粉状物与铁源前驱体溶液混合成浆状,搅拌后,加硅溶胶,加造孔剂,二次混合后,密封静置、干燥、焙烧,形成催化剂,其中以重量百分比计,含氧化铝50~90%,含氧化铜2~10%,含氧化铈5%~20%,含氧化铁为1~15%,硅溶胶以SiO2计2~5%。
2.根据权利要求1所述的铜基湿式氧化催化剂的制备方法,其特征在于,所述铝源前驱体为可溶性的铝盐和/或偏铝酸盐。
3.根据权利要求1所述的铜基湿式氧化催化剂的制备方法,其特征在于,所述铜源前驱体为可溶性的铜盐。
4.根据权利要求1所述的铜基湿式氧化催化剂的制备方法,其特征在于,所述pH为4~13。
5.根据权利要求1所述的铜基湿式氧化催化剂的制备方法,其特征在于,所述铈源前驱体为可溶性的铈盐。
6.根据权利要求1所述的铜基湿式氧化催化剂的制备方法,其特征在于,所述铁源前驱体为可溶性的铁盐。
7.根据权利要求1所述的铜基湿式氧化催化剂的制备方法,其特征在于,所述造孔剂是柠檬酸、尿素、三氯乙酸、活性炭、田菁粉一种或多种。
8.根据权利要求1所述的铜基湿式氧化催化剂的制备方法,其特征在于,所述焙烧的温度为400~850℃。
9.根据权利要求1所述的铜基湿式氧化催化剂的制备方法,其特征在于,所述pH为8~11。
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