CN108745345A - 一种无钒脱硝催化剂及其制备方法 - Google Patents
一种无钒脱硝催化剂及其制备方法 Download PDFInfo
- Publication number
- CN108745345A CN108745345A CN201810637002.XA CN201810637002A CN108745345A CN 108745345 A CN108745345 A CN 108745345A CN 201810637002 A CN201810637002 A CN 201810637002A CN 108745345 A CN108745345 A CN 108745345A
- Authority
- CN
- China
- Prior art keywords
- denitration catalyst
- vanadium
- vanadium denitration
- acid
- salt
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 43
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract 4
- 150000000703 Cerium Chemical class 0.000 claims description 12
- -1 transition metal salt Chemical class 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 claims description 2
- 230000009919 sequestration Effects 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims 2
- 238000003837 high-temperature calcination Methods 0.000 claims 2
- 229910017604 nitric acid Inorganic materials 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 235000019441 ethanol Nutrition 0.000 abstract description 10
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003750 conditioning effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000036541 health Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002019 doping agent Substances 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 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 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 241000040710 Chela Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B01J35/40—
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01D53/90—Injecting reactants
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- 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
- B01J23/70—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
- B01J23/70—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/30—Improvements relating to adipic acid or caprolactam production
Abstract
本发明公开了一种无钒脱硝催化剂，以CeO2纳米片为母体，过渡金属元素均匀掺入CeO2晶格中；本发明还公开了所述无钒脱硝催化剂的制备方法，包括：以氧化铈为主体，以过渡金属元素为掺杂剂，以常见碱金属溶液为调节剂，以邻苯二甲酸、联苯二甲酸、均苯三甲酸、均苯四甲酸等为配体，使其在水与乙醇的混合溶剂中进行螯合反应，螯合反应产物经干燥后，于400～700℃温度下，煅烧2～5h，得到无钒脱硝催化剂。该方法具有生产工艺简单、原料简单易得、易于工业化生产、采用无毒无害组分，对环境和人体健康无害等优势。本发明制得的无钒脱硝催化剂催化活性温度窗口宽，催化效率高，既可用于固定源工业脱硝也可用于移动源尾气脱硝。
Description
技术领域
本发明属于大气污染控制技术领域，具体涉及一种无钒脱硝催化剂及其制备方法。
背景技术
氮氧化物NOx是大气污染的重要污染物之一，它的存在会引起光化学烟雾、酸雨、温室效应等重大问题。NOx主要来源是化学燃料的燃烧，包括燃煤电厂、工业锅炉、机动车尾气、钢铁水泥厂等，其中燃煤电厂NOx的排放量占我国NOx总排放量的一半以上。
目前的脱硝技术包括选择性催化还原(SCR)、选择性非催化还原(SNCR)、低氮燃烧等。其中，选择性催化还原(SCR)脱硝技术是效率最高、最成熟、应用最广泛的废气脱硝技术，在国外电厂中已得到了广泛应用，市场占有率在70％以上，同时也成为我国废气脱硝的首选技术。
SCR催化剂是SCR技术的核心，其组分、结构、使用寿命及相关参数直接影响到SCR系统的整体脱硝效率。目前投入应用的SCR脱硝催化剂以V2O5-WO3/TiO2和V2O5-MoO3/TiO2为主，其脱硝最佳催化活性窗口范围为300～400℃之间，存在反应温度高、操作窗口窄、低温活性差、主要活性组分V2O5具有毒性等问题。
氧化铈(CeO2)具有优异的储氧性能及高氧化还原性，在SCR反应过程中得到广泛研究，多数情况下CeO2在脱硝催化剂领域多以活性组分存在，且需与主活性组分五氧化二钒V2O5配合使用。
如公开号为CN102350340A的中国专利文献公开了一种能够氧化零价汞的复合型烟气脱硝催化剂，其表达式为V2O5-CeO2-WO3/TiO2或V2O5-CeO2-MoO3/TiO2；其中，二氧化钛为载体，五氧化二钒V2O5为主活性组分，氧化铈CeO2为次活性组分，三氧化钨WO3或三氧化钼MoO3为助催化组分。虽然掺杂活性组分CeO2形成复合氧化物提高了脱硝催化剂的催化性能，但是其主活性组分仍然为具有毒性的V2O5，仍然没有解决目前投入应用的SCR脱硝催化剂具有钒毒性的问题。
专利号为CN103007919B的中国专利公开了一种氧化铈脱硝催化剂，其表达式为CeNaOx，各元素的摩尔比例为Ce:Na＝(90～98):(10～2)，x由各原子所带正负电子平衡确定。首次开发出了碱金属元素与稀土铈金属氧化物组成的无钒脱硝催化剂，对新型无钒SCR催化剂的研发具有重要意义。如何进一步拓展开发环保型无钒SCR催化剂，成为脱硝催化剂研究的一个重要课题。
发明内容
本发明提供了一种无钒脱硝催化剂，其催化活性温度窗口宽、催化效率高，本发明还提供了所述无钒脱硝催化剂的制备方法，操作简单、易行，成本低廉，适合工业化生产。
一种无钒脱硝催化剂，其化学组成为MxCeyO2，M为Ti、Fe、Co、Ni、Cu、Zr、Mo或Mn中至少一种；其中，x为0～5的正数，y为0～40的正数。所述的无钒脱硝催化剂以CeO2纳米片为母体，过渡金属元素均匀掺入CeO2晶格中。
本发明还提供了所述无钒脱硝催化剂的制备方法，操作简单、易行，包括：
取铈盐与过渡金属盐溶于水后，加入有机酸配体的醇溶液，其中水与醇的体积比为1:5～2:1，混合均匀后，调控体系温度为40～100℃，搅拌加入碱液调节反应体系的pH为2～5，搅拌反应1～5h，使铈盐、过渡金属盐与有机酸配体螯合反应完全，螯合反应产物经干燥后，于400～700℃温度下，煅烧2～5h，得到无钒脱硝催化剂。
所述的铈盐为含Ce的水溶性盐。
作为优选，所述的铈盐为硝酸铈、醋酸铈或硫酸铈中的至少一种。
所述的过渡金属盐为相应金属的水溶性盐。
作为优选，所述的过渡金属盐为钛酸四丁酯、硝酸锰、硝酸铁、硝酸钴、硝酸镍、硝酸铜、硝酸锆或硝酸钼中的一种或多种。
所述的有机酸配体为己二酸、对苯二甲酸、L-抗坏血酸、L-谷氨酸、邻苯二甲酸、联苯二甲酸或均苯四甲酸中的至少一种。
所述的铈盐和过渡金属盐的摩尔比为10～40:1。
所述的铈盐与有机酸配体的摩尔比为1:1～1.2。
所述的有机酸配体醇溶液中有机酸配体的浓度优选为5×10-5～2×10-4mM。
所述的醇为业内常用醇即可，如甲醇、乙醇、丙醇或乙二醇等。
所述的碱为常规碱，为碳酸钠、碳酸钾、氢氧化钠、氢氧化钾或氨水中的至少一种。
所述的搅拌速度为在500～800rpm。
作为优选，所述的螯合反应温度为50～90℃，反应时间为1～3h。
本发明提供的无钒脱硝催化剂是一种以氧化铈(CeO2)为主，以无钒过渡金属元素掺杂的复合型氧化物催化剂，呈薄均匀纳米片形貌，无活性组分团聚现象，催化剂具有较大比表面积，为催化反应提供更多的活性位点，催化效率最高可达95％。
另本发明制备的无钒脱硝催化剂性质稳定，加热至1100℃，30min以上催化剂结构没有任何变化，宽泛的催化活性温度窗口使其既可用于固定源工业脱硝也可用于移动源尾气脱硝。
与现有技术相比，本发明具有以下有益效果：
(1)本发明提供的制备方法，生产工艺简单，原料简单易得，易于工业化生产，采用无毒无害组分，对环境和人体健康无害；
(2)本发明提供的无钒脱硝催化剂的性质稳定，加热至1100℃，30min以上催化剂结构没有任何变化，宽泛的催化活性窗口使其既可用于固定源工业脱硝也可用于移动源尾气脱硝；
(3)本发明制备的复合型氧化物催化剂，活性组分掺杂均匀，内部的协同效应使催化剂具有较高催化性能，催化效率最高可达95％。
附图说明
图1为本发明实施例1中制得的无钒脱硝催化剂的SEM图。
图2为本发明实施例1中制得的无钒脱硝催化剂的XRD图。
图3为本发明实施例1中制得的无钒脱硝催化剂的脱硝转化率随温度变化曲线图。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明提供的一种无钒脱硝催化剂及其制备方法进行具体描述，但本发明并不限于这些实施例，该领域技术人员在本发明核心指导思想下做出的非本质改进和调整，仍然属于本发明的保护范围。
实施例1
将硝酸铈(0.3907g)与硝酸锰(12.55mg)、硝酸钴(14.55mg)溶于(20mL)水中，其中Ce3+与Co2+、Mn2+的摩尔比为18:1:1，室温800rpm搅拌30min，使其混合均匀。将联苯二甲酸(0.242g)溶于(10mL)乙醇中，将两种溶液混合，置于70℃油浴中加热，以氢氧化钠为调节剂，调节溶液pH为4，恒温2h。将螯合反应产物离心干燥，置于60℃烘箱中干燥，将干燥后的样品置于马弗炉中，600℃烧结2h，所得无钒脱硝催化剂是一种Co、Mn掺杂的CeO2复合型氧化物催化剂，其SEM如图1所示，XRD图如图2所示，收率为83％。
由图1-2可知，所得到的掺杂氧化物中杂元素均匀掺入氧化铈晶格中。
性能测试：
将实施例1制得的无钒脱硝催化剂放入微型石英反应器中，模拟的烟气中NO含量为500ppm，NH3含量为500ppm，O2的体积含量为5％，以N2为平衡气，反应温度为150～400℃，空速为120000mL(NO)g-1 (cat)h-1，脱硝效率计算公式：η＝([NO]入-[NO]出)/[NO]入*100％。当反应温度达350℃时，NO浓度为60ppm，此时转化率为88％。附图3为转化率-温度曲线。
实施例2
将硝酸铈(0.3038g)与硝酸锰(75mg)溶于10ml水中，其中Ce3+与Mn2+的摩尔比为7:3，室温500rpm搅拌30min，使其混合均匀。将邻苯二甲酸0.166g溶于(30ml)乙醇中，将两种溶液混合，置于50℃油浴中加热，以氢氧化钠为pH调节剂，调节溶液pH为3后，恒温2h。将螯合反应产物离心干燥，置于60℃烘箱中干燥，将干燥后的样品置于马弗炉中，400℃烧结4h，得Mn/CeO2复合型无钒脱硝催化剂，收率为70％。本发明实施例制备的脱硝催化剂脱硝效率为90％。
实施例3
将硝酸铈(0.3472g)与硝酸钴(58.2mg)溶于10ml水中，其中Ce3+与Co2+的摩尔比为8:2，室温800rpm搅拌30min，使其混合均匀。将邻苯二甲酸0.166g溶于40ml乙醇中，将两种溶液混合，置于50℃油浴中加热，以氢氧化钠为调节剂，调节溶液pH为4，恒温2h。将反应物离心干燥，置于60℃烘箱中干燥，将干燥后的样品置于马弗炉中，500℃烧结3h，得Co/CeO2复合型无钒脱硝催化剂，收率为80％。本发明实施例制备的脱硝催化剂脱硝效率为80％。
实施例4
将硝酸铈0.3906g与硝酸铜12.08mg、硝酸镍14.54mg溶于20ml水中，其中Ce3+与Cu2 +、Ni2+的摩尔比为18:1:1,室温800rpm搅拌30min,使其混合均匀。将联苯二甲酸0.2422g溶于100ml乙醇中，将两种溶液混合，置于70℃油浴中加热，以氢氧化钠为调节剂，调节溶液pH为2，恒温2h。将反应物离心干燥，置于60℃烘箱中干燥，将干燥后的样品置于马弗炉中，600℃烧结2h，得Cu、Ni掺杂的CeO2复合型无钒脱硝催化剂，收率为88％。本发明实施例制备的脱硝催化剂脱硝效率为95％。
实施例5
将硝酸铈0.3906g与硝酸锰12.55mg、硝酸镍7.27mg、硝酸铜6.04mg溶于50ml水中，其中Ce3+与Mn2+、Cu2+、Ni2+的摩尔比为36:2:1:1,室温600rpm搅拌30min,使其混合均匀。将联苯二甲酸0.2422g溶于25ml乙醇中，将两种溶液混合，置于70℃油浴中加热，以氨水为调节剂，调节溶液pH为2，恒温2h。将反应物离心干燥，置于60℃烘箱中干燥，将干燥后的样品置于马弗炉中，700℃烧结5h，得Cu、Ni、Mn三元掺杂的CeO2复合型无钒脱硝催化剂，收率为78％。本发明实施例制备的脱硝催化剂脱硝效率为75％。
Claims (9)
1.一种无钒脱硝催化剂，其化学组成为MxCeyO2，M为Ti、Fe、Co、Ni、Cu、Zr、Mo或Mn中至少一种；其中，x为0～5的正数，y为0～40的正数。
2.根据权利要求1所述的无钒脱硝催化剂，其特征在于，所述的无钒脱硝催化剂以CeO2纳米片为母体，过渡金属元素均匀掺入CeO2晶格中。
3.一种无钒脱硝催化剂的制备方法，包括：
取铈盐与过渡金属盐溶于水后，加入有机酸配体的醇溶液，混合均匀后，调控体系温度为40～100℃，搅拌加入碱液调节反应体系的pH为2～5，搅拌反应1～5h，使铈盐、过渡金属盐与配体螯合反应完全，螯合反应产物经干燥后，高温煅烧得无钒脱硝催化剂。
4.根据权利要求3所述的无钒脱硝催化剂的制备方法，其特征在于，所述的铈盐为含Ce的水溶性盐；所述的过渡金属盐为相应金属的水溶性盐。
5.根据权利要求4所述的无钒脱硝催化剂的制备方法，其特征在于，所述的铈盐为硝酸铈、醋酸铈或硫酸铈中的至少一种；所述的过渡金属盐为钛酸四丁酯、硝酸锰、硝酸铁、硝酸钴、硝酸镍、硝酸铜、硝酸锆或硝酸钼中的一种或多种。
6.根据权利要求3所述的无钒脱硝催化剂的制备方法，其特征在于，所述的有机酸配体为己二酸、对苯二甲酸、L-抗坏血酸、L-谷氨酸、邻苯二甲酸、均苯三甲酸、联苯二甲酸或均苯四甲酸中的至少一种。
7.根据权利要求3所述的无钒脱硝催化剂的制备方法，其特征在于，所述的铈盐和过渡金属盐的摩尔比为1～40:1；所述的铈盐与有机酸配体的摩尔比为1:1～1.2。
8.根据权利要求3所述的无钒脱硝催化剂的制备方法，其特征在于，所述溶液中水与醇的体积比为1:5～2:1。
9.根据权利要求3所述的无钒脱硝催化剂的制备方法，其特征在于，所述高温煅烧温度为400～700℃，煅烧时间为2～5h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810637002.XA CN108745345A (zh) | 2018-06-20 | 2018-06-20 | 一种无钒脱硝催化剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810637002.XA CN108745345A (zh) | 2018-06-20 | 2018-06-20 | 一种无钒脱硝催化剂及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108745345A true CN108745345A (zh) | 2018-11-06 |
Family
ID=63979242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810637002.XA Pending CN108745345A (zh) | 2018-06-20 | 2018-06-20 | 一种无钒脱硝催化剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108745345A (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529859A (zh) * | 2018-12-19 | 2019-03-29 | 济南大学 | 一种用于汽车尾气催化净化的多功能介孔铈基固溶体催化剂 |
| CN110354839A (zh) * | 2019-08-20 | 2019-10-22 | 北京晨晰环保工程有限公司 | 一种铈基复合金属氧化物纳米花材料及其制备方法与应用 |
| CN113976102A (zh) * | 2021-11-29 | 2022-01-28 | 中国科学院兰州化学物理研究所 | 一种低温稀土基脱硝催化剂粉体及其制备方法 |
| CN114735742A (zh) * | 2022-03-18 | 2022-07-12 | 清华大学 | 掺杂型纳米氧化物材料及其制备方法和应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319570A (zh) * | 2011-07-08 | 2012-01-18 | 厦门大学 | 一氧化碳氧化的三元复合氧化物催化剂及其制备方法 |
| CN104474890A (zh) * | 2014-12-05 | 2015-04-01 | 湘潭大学 | 一种负载型金属氧化物催化剂催化直接分解no脱硝的方法 |
| CN105664910A (zh) * | 2016-03-02 | 2016-06-15 | 南京理工大学 | 掺杂型铈钛催化剂的制备方法 |
| CN105983403A (zh) * | 2015-02-09 | 2016-10-05 | 有研稀土新材料股份有限公司 | 一种铈锆复合氧化物、其制备方法及催化剂的应用 |
-
2018
- 2018-06-20 CN CN201810637002.XA patent/CN108745345A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319570A (zh) * | 2011-07-08 | 2012-01-18 | 厦门大学 | 一氧化碳氧化的三元复合氧化物催化剂及其制备方法 |
| CN104474890A (zh) * | 2014-12-05 | 2015-04-01 | 湘潭大学 | 一种负载型金属氧化物催化剂催化直接分解no脱硝的方法 |
| CN105983403A (zh) * | 2015-02-09 | 2016-10-05 | 有研稀土新材料股份有限公司 | 一种铈锆复合氧化物、其制备方法及催化剂的应用 |
| CN105664910A (zh) * | 2016-03-02 | 2016-06-15 | 南京理工大学 | 掺杂型铈钛催化剂的制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| FENGYU GAO等: "Promotional mechanisms of activity and SO2 tolerance of Co- or Ni-doped MnOx-CeO2 catalysts for SCR of NOx with NH3 at low temperature", 《CHEMICAL ENGINEERING JOURNAL》 * |
| GONGSHIN QI等: "Characterization and FTIR Studies of MnOx-CeO2 Catalyst for Low-Temperature Selective Catalytic Reduction of NO with NH3", 《J. PHYS. CHEM. B》 * |
| XIA ZHOU等: "Fabrication of homogeneously Cu2+/La3+-doped CeO2 nanosheets and their application in CO oxidation", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529859A (zh) * | 2018-12-19 | 2019-03-29 | 济南大学 | 一种用于汽车尾气催化净化的多功能介孔铈基固溶体催化剂 |
| CN110354839A (zh) * | 2019-08-20 | 2019-10-22 | 北京晨晰环保工程有限公司 | 一种铈基复合金属氧化物纳米花材料及其制备方法与应用 |
| CN110354839B (zh) * | 2019-08-20 | 2022-11-18 | 北京晨晰环保工程有限公司 | 一种铈基复合金属氧化物纳米花材料及其制备方法与应用 |
| CN113976102A (zh) * | 2021-11-29 | 2022-01-28 | 中国科学院兰州化学物理研究所 | 一种低温稀土基脱硝催化剂粉体及其制备方法 |
| CN114735742A (zh) * | 2022-03-18 | 2022-07-12 | 清华大学 | 掺杂型纳米氧化物材料及其制备方法和应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108745345A (zh) | 一种无钒脱硝催化剂及其制备方法 | |
| CN101966451B (zh) | 一种选择性催化氧化氨的纳米铈锆固溶体基催化剂的制备方法及应用 | |
| CN108722477B (zh) | 一种抗碱中毒高效脱硝催化剂及其制备方法和应用 | |
| CN101590404B (zh) | 一种低钒脱硝催化剂及其制备方法和应用 | |
| CN104525216B (zh) | 用于宽温度窗口高硫条件下的脱硝催化剂及其制备方法 | |
| CN102658161B (zh) | 一种负载型铁基复合氧化物催化剂及其制备方法 | |
| CN103230813A (zh) | 一种适用于水泥窑炉的抗碱中毒的脱硝催化剂的制备方法 | |
| CN106732799A (zh) | 一种新型低温脱硝mof催化剂及其制备方法 | |
| CN102773090A (zh) | Wo3新型添加工艺的整体蜂窝式脱硝催化剂及其制备方法 | |
| CN107649116A (zh) | 铈锡复合氧化物脱硝催化剂及其制备方法和应用 | |
| CN104941655B (zh) | 一种新型铁钨复合氧化物脱硝催化剂及其制备和应用 | |
| CN105797714B (zh) | 一种钬改性的锰钛复合氧化物低温脱硝催化剂及其制备方法 | |
| CN105833901A (zh) | 一种PrOx-MnOx/SAPO-34低温SCR烟气脱硝催化剂及其制备方法与应用 | |
| CN112742413B (zh) | 一种低温scr脱硝催化剂及其制备方法和应用 | |
| CN105289644A (zh) | 一种平板式抗硫低温scr脱硝催化剂及其制备方法 | |
| CN109092324A (zh) | 低温scr烟气脱硝催化剂及其制备方法和应用 | |
| CN103263913B (zh) | 一种适用于水泥窑炉的高比表面抗碱中毒脱硝催化剂的制备方法 | |
| CN108579728A (zh) | 一种高热稳定性氨选择性还原氮氧化物的催化剂及制备方法 | |
| CN106513005A (zh) | 一种铁基复合氧化物催化剂的制备方法 | |
| CN114210320A (zh) | 一种异质双原子低温耐硫scr催化剂及其制备方法 | |
| CN107185523B (zh) | 一种钬改性的脱硝催化剂的制备方法及其产品 | |
| CN102101049A (zh) | 一种中温抗硫型复合氧化物催化剂及其制备和应用 | |
| CN104324728B (zh) | 尾气净化用的介孔复合氧化物催化剂及其制备方法 | |
| CN111068709A (zh) | 一种铁锰催化剂的制备方法 | |
| CN112569952A (zh) | 一种掺杂钐的氧化铁scr脱硝催化剂及其制备方法与应用 |
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: 20181106 |