CN109603804B - A kind of while denitration demercuration takes off dioxin rare-earth base catalyst and preparation method and application - Google Patents
A kind of while denitration demercuration takes off dioxin rare-earth base catalyst and preparation method and application Download PDFInfo
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- CN109603804B CN109603804B CN201811602921.XA CN201811602921A CN109603804B CN 109603804 B CN109603804 B CN 109603804B CN 201811602921 A CN201811602921 A CN 201811602921A CN 109603804 B CN109603804 B CN 109603804B
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- erbium
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 16
- -1 dioxin rare-earth Chemical class 0.000 title claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003426 co-catalyst Substances 0.000 claims abstract description 56
- 239000000654 additive Substances 0.000 claims abstract description 52
- 230000000996 additive effect Effects 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 47
- 238000000465 moulding Methods 0.000 claims abstract description 40
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 17
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical class [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 10
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 64
- 239000008367 deionised water Substances 0.000 claims description 45
- 229910021641 deionized water Inorganic materials 0.000 claims description 45
- 235000010323 ascorbic acid Nutrition 0.000 claims description 30
- 239000011668 ascorbic acid Substances 0.000 claims description 30
- 229960005070 ascorbic acid Drugs 0.000 claims description 30
- 229910001868 water Inorganic materials 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 13
- 150000000703 Cerium Chemical class 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 150000002696 manganese Chemical class 0.000 claims description 11
- 150000003746 yttrium Chemical class 0.000 claims description 11
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 9
- 150000000917 Erbium Chemical class 0.000 claims description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical group S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical group [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 3
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims 4
- 150000003839 salts Chemical class 0.000 claims 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims 2
- 229930003268 Vitamin C Natural products 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 2
- 150000002910 rare earth metals Chemical class 0.000 claims 2
- 235000019154 vitamin C Nutrition 0.000 claims 2
- 239000011718 vitamin C Substances 0.000 claims 2
- YFVKHKCZBSGZPE-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(propylamino)propan-1-one Chemical compound CCCNC(C)C(=O)C1=CC=C2OCOC2=C1 YFVKHKCZBSGZPE-UHFFFAOYSA-N 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 235000010980 cellulose Nutrition 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229920000609 methyl cellulose Polymers 0.000 claims 1
- 239000001923 methylcellulose Substances 0.000 claims 1
- 235000010981 methylcellulose Nutrition 0.000 claims 1
- 238000005457 optimization Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 35
- 238000011156 evaluation Methods 0.000 description 20
- 238000004088 simulation Methods 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000012159 carrier gas Substances 0.000 description 11
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 10
- 230000004044 response Effects 0.000 description 10
- 239000003546 flue gas Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- IVRVGCUEJLYELA-UHFFFAOYSA-K trichloroerbium;hydrate Chemical compound O.Cl[Er](Cl)Cl IVRVGCUEJLYELA-UHFFFAOYSA-K 0.000 description 6
- BEDFIBPNPHRGDO-UHFFFAOYSA-N yttrium;hydrate Chemical compound O.[Y] BEDFIBPNPHRGDO-UHFFFAOYSA-N 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- ISEXWJYBJMXWCC-UHFFFAOYSA-N erbium;hydrate Chemical compound O.[Er] ISEXWJYBJMXWCC-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- 229920003091 Methocel™ Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- B01J23/10—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
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- 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
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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
- B01J23/16—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
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of denitration demercurations simultaneously to take off dioxin rare-earth base catalyst and its preparation method and application, using cerium oxide and erbium oxide as catalytic active component, using the mixture in zirconium oxide and/or yttrium oxide and/or manganese oxide as co-catalyst, the titanium dioxide sub-micron ball of modified butyl titanate generation is optimized as main carriers using hydrochloric acid.By active component and co-catalyst presoma composite solution, optimize modified catalyst carrier and organic molding additive stir evenly, be kneaded, is aging, extrusion molding, be made through drying, roasting.The catalyst is environmental-friendly, can take off dioxin by NO_x Reduction by Effective demercuration simultaneously, active temperature section is wide, high mechanical strength, SO2Oxidation efficiency it is low, it is at low cost.Denitration and de- dioxin efficiency are all larger than 90% in 220-400 DEG C, and demercuration efficiency is all larger than 95%.The product is widely portable to the fields such as coal-burning power plant, chemical plant.
Description
Technical field
The present invention relates to a kind of denitration demercurations simultaneously to take off dioxin rare-earth base catalyst and its preparation method and application, belongs to
Environment protection catalytic material and air contaminant treatment field, using the product of this method preparation especially suitable for coal-burning power plant, chemical plant
Equal fields gas cleaning.
Background technique
Nitrogen oxides (NOx) it is one of origin causes of formation of pollutants such as haze, acid rain, mercury can cause brokenly the nervous system of people
It is bad, especially 2,3,7,8- tetra- chloro hexichol of dioxin-simultaneously-to dioxin (2,3,7,8-TCDD), then be hitherto known
The strongest pollutant of toxicity, these three types of atmosphere pollutions can all seriously endanger human health and ecological environment.Make coal-burning power plant
For NOxMaximum fixed discharge source, can also generate micro nonvalent mercury and trace dioxin, become the emphasis row of air contaminant treatment
Industry.With the smooth progress implemented with strategic plans such as blue sky defended wars of " prevention and control of air pollution action plan ", three kinds of pollutions
The minimum discharge of object is imperative, and wherein emission limits of nitrogen oxides must not be higher than 150mg/m3, dioxins concentration must not be higher than
0.1ng TEQ/m3, mercury and mercuric compounds content must not be higher than 0.05mg/m3.The flue gas of the industrial discharges such as coal-burning power plant is dirty at present
Object complicated component is contaminated, the difficulty of purification work is not only increased, it can also be because being segmented independent process NOx, mercury and dioxin cause work
Industry cost is significantly increased, therefore removing is the master of smoke gas treatment from now on to realize that function is integrated while multiple pollutant
Flow developing direction.For denitrating flue gas, selective catalytic reduction (SCR) denitration technology is high-efficient, stability is good, becomes domestic and international
The mainstream technology and developing direction of industrial applied research, SCR technology core are denitrating catalyst.Although common catalytic component based on vanadium was both
Can denitration can also take off dioxin, but be applied to simultaneously denitration take off dioxin when will appear the two catalytic temperature window it is inconsistent
The problem of, and then need additionally to spray into hydrogen chloride in flue gas when common vanadium base or cerium base catalyst while denitration demercuration, occur
The problem of hydrogen chloride and ammonia competitive Adsorption.Therefore research and development can simultaneously denitration demercuration take off dioxin catalyst be have reality
The important directions of meaning and theory demands.
Have individual patents both at home and abroad and discloses the catalyst and preparation method thereof that low temperature collaboration denitration takes off dioxin demercuration.
Patent (CN201711348073.X) uses metatitanic acid, sulphation palygorskite for carrier, and copper oxide, manganese oxide, vanadium oxide are to live
Property component, rare-earth oxide be coagent be made a kind of low temperature cooperate with denitration take off dioxin demercuration honeycombed catalyst and
Preparation method, the catalyst are mainly 80~300 DEG C using flue-gas temperature, but it is not only containing the vanadium oxide of hypertoxicity, low
The application conditions of temperature also result in manganese oxide and vanadium oxide because sulfur poisoning inactivates；Patent (CN201410467857.4) is with titanium dioxide
Titanium, montmorillonite are carrier, are made a kind of dilute using ammonium metatungstate, cerous nitrate and lanthanum nitrate as active component, under the action of auxiliary material
Soil matrix high intensity, anti-oxidant catalyst for denitrating flue gas, but its complex process, long preparation period, need to be kneaded and repeatedly do for six times
It is dry, and drying time is up to 8-12 days, in addition it does not provide practical demercuration and de- dioxin efficiency.Although above two catalyst
Dioxin can be taken off by denitration demercuration simultaneously, but because need to additionally spray when high production cost or substance containing hypertoxicity and unresolved demercuration
The problems such as entering hydrogen chloride, and can not really be applied to the industrial circles such as coal-burning power plant.
Summary of the invention
The purpose of the present invention is taking off the current situation and existing problems of dioxin for the industrial denitration demercuration such as existing coal-burning power plant,
And a kind of de- dioxin rare-earth base catalyst of denitration demercuration simultaneously is proposed, it is a further object of the present invention to provide above-mentioned catalyst
Preparation method, especially suitable for the fields gas cleaning such as coal-burning power plant, chemical plant.
The technical solution of the present invention is as follows: a kind of denitration demercuration simultaneously takes off the preparation method of dioxin rare-earth base catalyst,
It is characterized in that using cerium oxide and erbium oxide as catalytic active component, with the mixing in zirconium oxide and/or yttrium oxide and/or manganese oxide
Object is co-catalyst, optimizes the titanium dioxide sub-micron ball of modified butyl titanate generation as carrier using hydrochloric acid.With carrier quality
On the basis of, the mass percentage of active component is 1%~10%, and the mass percentage of co-catalyst is 0.5%~5%.
It is preferred that the mass ratio of cerium oxide and erbium oxide is 1:(0.01~0.3 in above-mentioned active component).
It is specific to walk the present invention also provides the preparation method that above-mentioned while denitration demercuration takes off dioxin rare-earth base catalyst
Suddenly are as follows:
(1) preparation of active component precursor solution
Suitable cerium salt, erbium salt and ascorbic acid are weighed, deionized water is added and is placed in thermostat water bath stirring until solution
In clear shape and viscosity reaches 500-1000cP, obtains solution A.Wherein cerium salt and erbium salt/ascorbic acid/deionized water
Mass ratio is 1:0.2:(1~5).
(2) co-catalyst presoma solion configures
It weighs the mixture in zirconates and/or yttrium salt and/or manganese salt and appropriate ascorbic acid and deionized water mixing is added；
It is placed in thermostat water bath to stir evenly until solution is in clear shape and viscosity reaches 500-1000cP, obtains solution B, be made
Co-catalyst presoma solion；Wherein mixture/ascorbic acid/deionized water in zirconates and/or yttrium salt and/or manganese salt
Mass ratio be 1:0.2:(1~5).
(3) preparation of carrier
Appropriate butyl titanate, hydrochloric acid and water are measured, is placed in hydrothermal reaction kettle, with 180 DEG C of hydro-thermal 2h, through filtering, very
Sky is dried to obtain hydrochloric acid and optimizes modified titanium dioxide sub-micron ball carrier.Wherein concentration of hydrochloric acid be 2.5M, butyl titanate/
Hydrochloric acid/deionized water volume ratio is 1:2:10.
(4) weighing for additive is formed
Weigh molding additive；
(5) on the basis of carrier quality, by active component oxide, co-catalyst oxide and molding additive difference
The mass percent for accounting for carrier quality is 1~10%, 0.5~5% and 0.5~0.8%, by active component made from step (1)
The mixing of co-catalyst presoma solion B made from presoma solion A and step (2), after stirring, then with step
(4) weighed additive is added together in carrier made from step (3), and stirring pugging is put in air dry oven after aging
Heat preservation and dryness obtains catalyst green body.
(6) roasting of catalyst
Catalyst green body made from step (5) is placed in Muffle furnace to roast under oxidizing atmosphere and denitration demercuration simultaneously is made
De- dioxin rare-earth base catalyst.
Cerium salt described in preferred steps (1) is cerous nitrate or cerium chloride；The erbium salt is erbium nitrate or erbium chloride；Step
Suddenly manganese salt described in (2) is manganese nitrate；The zirconates is zirconium oxychloride；The yttrium salt is yttrium nitrate or yttrium chloride.
The temperature of thermostat water bath described in preferred steps (1) and (2) be 50~60 DEG C, mixing time be 30~
60min。
Titanium source described in preferred steps (3) is butyl titanate；The hydrochloric acid is 2.5M concentration.
Molding additive described in preferred steps (4) be carboxylic propyl methocel, carboxymethyl cellulose, glycerine or
One or more of acetamide.
Mixing time described in preferred steps (5) is 10~20min；The drying temperature is 80~110 DEG C, dry
Time is 2~4h；Maturing temperature in step (6) is 500~600 DEG C, keeps the temperature 1.5~3h.
Application of the catalyst described in technical solution of the present invention in terms of denitration demercuration takes off dioxin.
Catalytic reaction condition and result of the invention: 10mL catalyst sample is taken to be packed into catalyst performance evaluation reaction unit
In, quartzy bore is 10mm in evaluation response device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation are as follows:
NO(600ppm)、NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2For
Carrier gas, catalyst grain size are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.
Denitration and de- dioxin efficiency are all larger than 90% in 220-400 DEG C, and demercuration efficiency is all larger than 95%.
The utility model has the advantages that
The de- dioxin of denitration demercuration is high-efficient simultaneously for catalyst prepared by the present invention, and active temperature section is wide, in 220-
Catalytic activity while having efficient in 400 DEG C.It is compared with the prior art, which not only can be by NOxWith
Dioxin catalysis generates N2、HCl、CO2And H2O, the HCl of generation and the Cl ion on catalyst sample surface are alternatively arranged as demercuration
Auxiliary agent does not need additionally to spray into HCl, solves the problems, such as catalyst surface acidic and alkaline gas competitive Adsorption, while because of catalyst
Carrier optimizes modified rear surface through hydrochloric acid and contains Cl ion, reduces sour gas such as SO2Absorption possibility, therefore catalyst
To SO in flue gas2Oxidation efficiency substantially reduce so that catalyst have excellent sulfur poisoning resistance.In addition, this is urged
Agent component is environmental-friendly, and preparation process is simple, and cost is relatively low, and cost performance is high, while mechanical strength with higher, can be effective
The investment cost and operating cost of the industry such as coal-burning power plant is reduced, it is net especially suitable for the fields such as coal-burning power plant, chemical plant flue gas
Change, there is stronger application and popularization value.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto: embodiment 1
(1) preparation of active component precursor solution
Six nitric hydrate cerium of 2.498g, six nitric hydrate erbium of 0.024g and 0.504g ascorbic acid are weighed, 12.610g is added
Deionized water is placed in 50 DEG C of thermostat water baths stirring 30min and reaches 500cP in clear shape and viscosity to solution, obtains activity
Component precursor solution；
(2) co-catalyst presoma solion configures
It weighs 13.076g eight and is hydrated zirconium oxychloride and 2.615g ascorbic acid, 13.076g deionized water is added and is placed in 60 DEG C
Thermostat water bath stirs 60min and reaches 1000cP in clear shape and viscosity to solution, obtains co-catalyst presoma ion
Solution；
(3) preparation of catalyst carrier
It measures 5mL butyl titanate, the hydrochloric acid and 50mL deionized water that 10mL concentration is 2.5M, is placed in hydrothermal reaction kettle
In, it with 180 DEG C of hydro-thermal 2h, filtered, be dried in vacuo, obtained hydrochloric acid and optimize modified titanium dioxide sub-micron ball carrier, it is more
Secondary repeat the above steps total prepares carrier 100g.
(4) weighing for additive is formed
0.500g carboxylic propyl methocel is weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 1%, 5%, 0.5%, and active component solution made from step (1) and step (2) is obtained
The mixing of co-catalyst presoma solion, stirs 10min, step (3) then is added together with step (4) weighed additive
Carrier obtained, stirring pugging are put in heat preservation and dryness 2h in 80 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 500 DEG C of roasting 1.5h in Muffle furnace in air atmosphere, sample is made
Product；
(7) catalytic activity is tested: taking 10mL catalyst sample to be fitted into catalyst performance evaluation reaction unit, evaluation response
Quartzy bore is 10mm in device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation are as follows: NO (600ppm),
NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2For carrier gas, catalyst
Granularity are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.It is taken off in 220-400 DEG C
Nitre and de- dioxin efficiency minimum 90.5%, demercuration efficiency minimum 95.8%.
Embodiment 2:
(1) preparation of active component precursor solution
11.015g anhydrous cerium chloride, six chloride hydrate erbium of 4.679g and 3.139g ascorbic acid are weighed, 15.694g is added
Deionized water is placed in 60 DEG C of thermostat water baths stirring 60min and reaches 1000cP in clear shape and viscosity to solution, is lived
Property component precursor solution；
(2) co-catalyst presoma solion configures
2.058g manganese nitrate (50wt.%) solution and 0.412g ascorbic acid are weighed, 2.058g deionized water is added and is placed in
50 DEG C of thermostat water baths stir 30min and reach 500cP in clear shape and viscosity to solution, obtain co-catalyst presoma from
Sub- solution；
(3) preparation of catalyst carrier
It measures 5mL butyl titanate, the hydrochloric acid and 50mL deionized water that 10mL concentration is 2.5M, is placed in hydrothermal reaction kettle
In, it with 180 DEG C of hydro-thermal 2h, filtered, be dried in vacuo, obtained hydrochloric acid and optimize modified titanium dioxide sub-micron ball carrier, it is more
Secondary repeat the above steps total prepares carrier 100g.
(4) weighing for additive is formed
0.500g carboxymethyl cellulose and 0.300g glycerine are weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 10%, 0.5%, 0.8%, and active component solution made from step (1) and step (2) are made
The mixing of co-catalyst presoma, stir 20min, it is obtained that step (3) be then added together with step (4) weighed additive
Carrier, stirring pugging are put in heat preservation and dryness 4h in 110 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 600 DEG C of roasting 3h in Muffle furnace in air atmosphere, sample is made；
(7) catalytic activity is tested: taking 10mL catalyst sample to be fitted into catalyst performance evaluation reaction unit, evaluation response
Quartzy bore is 10mm in device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation are as follows: NO (600ppm),
NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2For carrier gas, catalyst
Granularity are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.It is taken off in 220-400 DEG C
Nitre and de- dioxin efficiency minimum 91.2%, demercuration efficiency minimum 95.1%.
Embodiment 3:
(1) preparation of active component precursor solution
11.015g anhydrous cerium chloride, six chloride hydrate erbium of 4.679g and 3.139g ascorbic acid are weighed, 15.694g is added
Deionized water is placed in 60 DEG C of thermostat water baths stirring 60min and reaches 1000cP in clear shape and viscosity to solution, is lived
Property component precursor solution；
(2) co-catalyst presoma solion configures
Six nitric hydrate yttrium of 16.964g and 3.393g ascorbic acid are weighed, 16.964g deionized water is added and is placed in 60 DEG C of perseverances
Warm water bath stirs 60min and reaches 1000cP in clear shape and viscosity to solution, and it is molten to obtain co-catalyst presoma ion
Liquid；
(3) preparation of catalyst carrier
It measures 5mL butyl titanate, the hydrochloric acid and 50mL deionized water that 10mL concentration is 2.5M, is placed in hydrothermal reaction kettle
In, it with 180 DEG C of hydro-thermal 2h, filtered, be dried in vacuo, obtained hydrochloric acid and optimize modified titanium dioxide sub-micron ball carrier, it is more
Secondary repeat the above steps total prepares carrier 100g.
(4) weighing for additive is formed
0.300g carboxymethyl cellulose and 0.200g acetamide are weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 10%, 5%, 0.5%, and active component solution made from step (1) and step (2) is obtained
The mixing of co-catalyst presoma, stirs 20min, and step (3) load obtained is then added together with step (4) weighed additive
Body, stirring pugging are put in heat preservation and dryness 4h in 80 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 600 DEG C of roasting 1.5h in Muffle furnace in air atmosphere, sample is made
Product；
(7) catalytic activity is tested: catalytic activity test: 10mL catalyst sample being taken to be packed into catalyst performance evaluation reaction dress
In setting, quartzy bore is 10mm in evaluation response device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation
Are as follows: NO (600ppm), NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2
For carrier gas, catalyst grain size are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.
Denitration and de- dioxin efficiency minimum 93.8%, demercuration efficiency minimum 97.5% in 220-400 DEG C.
Embodiment 4
(1) preparation of active component precursor solution
11.015g anhydrous cerium chloride, six chloride hydrate erbium of 4.679g and 3.139g ascorbic acid are weighed, 15.694g is added
Deionized water is placed in 60 DEG C of thermostat water baths stirring 60min and reaches 500cP in clear shape and viscosity to solution, obtains activity
Component precursor solution；
(2) co-catalyst presoma solion configures
0.866g is weighed without hydration yttrium chloride and 0.173g ascorbic acid, 4.330g deionized water is added and is placed in 60 DEG C of constant temperature
Water-bath stirs 60min and reaches 500cP in clear shape and viscosity to solution, obtains co-catalyst presoma solion；
(3) preparation of catalyst carrier
It measures 5mL butyl titanate, the hydrochloric acid and 50mL deionized water that 10mL concentration is 2.5M, is placed in hydrothermal reaction kettle
In, it with 180 DEG C of hydro-thermal 2h, filtered, be dried in vacuo, obtained hydrochloric acid and optimize modified titanium dioxide sub-micron ball carrier, it is more
Secondary repeat the above steps total prepares carrier 100g.
(4) weighing for additive is formed
0.300g carboxymethyl cellulose and 0.200g acetamide are weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 10%, 0.5%, 0.5%, and active component solution made from step (1) and step (2) are made
The mixing of co-catalyst presoma, stir 20min, it is obtained that step (3) be then added together with step (4) weighed additive
Carrier, stirring pugging are put in heat preservation and dryness 4h in 80 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 600 DEG C of roasting 1.5h in Muffle furnace in air atmosphere, sample is made
Product；
(7) catalytic activity is tested: catalytic activity test: 10mL catalyst sample being taken to be packed into catalyst performance evaluation reaction dress
In setting, quartzy bore is 10mm in evaluation response device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation
Are as follows: NO (600ppm), NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2
For carrier gas, catalyst grain size are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.
Denitration and de- dioxin efficiency minimum 91.7%, demercuration efficiency minimum 95.1% in 220-400 DEG C.
Embodiment 5
(1) preparation of active component precursor solution
Six nitric hydrate cerium of 2.498g, six nitric hydrate erbium of 0.024g and 0.504g ascorbic acid are weighed, 12.610g is added
Deionized water is placed in 50 DEG C of thermostat water baths stirring 30min and reaches 1000cP in clear shape and viscosity to solution, is lived
Property component precursor solution；
(2) co-catalyst presoma solion configures
It weighs 6.538g eight and is hydrated zirconium oxychloride, six nitric hydrate yttrium of 8.482g and 3.004g ascorbic acid, be added
15.020g deionized water is placed in 60 DEG C of thermostat water baths stirring 60min and reaches 1000cP in clear shape and viscosity to solution,
Obtain co-catalyst presoma solion；
(3) preparation of catalyst carrier
It measures 5mL butyl titanate, the hydrochloric acid and 50mL deionized water that 10mL concentration is 2.5M, is placed in hydrothermal reaction kettle
In, it with 180 DEG C of hydro-thermal 2h, filtered, be dried in vacuo, obtained hydrochloric acid and optimize modified titanium dioxide sub-micron ball carrier, it is more
Secondary repeat the above steps total prepares carrier 100g.
(4) weighing for additive is formed
0.800g glycerine is weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 1%, 5%, 0.8%, and active component solution made from step (1) and step (2) is obtained
The mixing of co-catalyst presoma solion, stirs 10min, step (3) then is added together with step (4) weighed additive
Carrier obtained, stirring pugging are put in heat preservation and dryness 2h in 80 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 500 DEG C of roasting 1.5h in Muffle furnace in air atmosphere, sample is made
Product；
(7) catalytic activity is tested: catalytic activity test: 10mL catalyst sample being taken to be packed into catalyst performance evaluation reaction dress
In setting, quartzy bore is 10mm in evaluation response device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation
Are as follows: NO (600ppm), NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2
For carrier gas, catalyst grain size are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.
Denitration and de- dioxin efficiency minimum 90.1%, demercuration efficiency minimum 95.3% in 220-400 DEG C.
Embodiment 6
(1) preparation of active component precursor solution
11.015g anhydrous cerium chloride, six chloride hydrate erbium of 4.679g and 3.139g ascorbic acid are weighed, 15.694g is added
Deionized water is placed in 60 DEG C of thermostat water baths stirring 60min and reaches 500cP in clear shape and viscosity to solution, obtains activity
Component precursor solution；
(2) co-catalyst presoma solion configures
It weighs 6.538g eight and is hydrated zirconium oxychloride, 10.290g manganese nitrate (50wt.%) solution and 3.366g ascorbic acid,
Addition 16.828g deionized water is placed in 60 DEG C of thermostat water baths stirring 60min and reaches to solution in clear shape and viscosity
1000cP obtains co-catalyst presoma solion；
(3) preparation of catalyst carrier
It measures 5mL butyl titanate, the hydrochloric acid and 50mL deionized water that 10mL concentration is 2.5M, is placed in hydrothermal reaction kettle
In, it with 180 DEG C of hydro-thermal 2h, filtered, be dried in vacuo, obtained hydrochloric acid and optimize modified titanium dioxide sub-micron ball carrier, it is more
Secondary repeat the above steps total prepares carrier 100g.
(4) weighing for additive is formed
0.500g acetamide is weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 10%, 5%, 0.5%, and active component solution made from step (1) and step (2) is obtained
The mixing of co-catalyst presoma, stirs 20min, and step (3) load obtained is then added together with step (4) weighed additive
Body, stirring pugging are put in heat preservation and dryness 4h in 80 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 600 DEG C of roasting 1.5h in Muffle furnace in air atmosphere, sample is made
Product；
(7) catalytic activity is tested: catalytic activity test: 10mL catalyst sample being taken to be packed into catalyst performance evaluation reaction dress
In setting, quartzy bore is 10mm in evaluation response device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation
Are as follows: NO (600ppm), NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2
For carrier gas, catalyst grain size are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.
Denitration and de- dioxin efficiency minimum 95.3%, demercuration efficiency minimum 98.4% in 220-400 DEG C.
Embodiment 7
(1) preparation of active component precursor solution
Six nitric hydrate cerium of 2.494g, six nitric hydrate erbium of 0.026g and 0.504g ascorbic acid are weighed, 12.600g is added
Deionized water is placed in 50 DEG C of thermostat water baths stirring 30min and reaches 1000cP in clear shape and viscosity to solution, is lived
Property component precursor solution；
(2) co-catalyst presoma solion configures
Six nitric hydrate yttrium of 8.482g, 10.290g manganese nitrate (50wt.%) solution and 3.754g ascorbic acid are weighed, is added
Enter 18.772g deionized water and be placed in 60 DEG C of thermostat water baths and stir 60min and reaches to solution in clear shape and tool viscosity
500cP obtains co-catalyst presoma solion；
(3) preparation of catalyst carrier
It measures 5mL butyl titanate, the hydrochloric acid and 50mL deionized water that 10mL concentration is 2.5M, is placed in hydrothermal reaction kettle
In, it with 180 DEG C of hydro-thermal 2h, filtered, be dried in vacuo, obtained hydrochloric acid and optimize modified titanium dioxide sub-micron ball carrier, it is more
Secondary repeat the above steps total prepares carrier 100g.
(4) weighing for additive is formed
0.800g glycerine is weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 1%, 5%, 0.8%, and active component solution made from step (1) and step (2) is obtained
The mixing of co-catalyst presoma solion, stirs 10min, step (3) then is added together with step (4) weighed additive
Carrier obtained, stirring pugging are put in heat preservation and dryness 2h in 80 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 500 DEG C of roasting 1.5h in Muffle furnace in air atmosphere, sample is made
Product；
(7) catalytic activity is tested: catalytic activity test: 10mL catalyst sample being taken to be packed into catalyst performance evaluation reaction dress
In setting, quartzy bore is 10mm in evaluation response device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation
Are as follows: NO (600ppm), NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2
For carrier gas, catalyst grain size are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.
Denitration and de- dioxin efficiency minimum 91.1%, demercuration efficiency minimum 96.5% in 220-400 DEG C.
Embodiment 8
(1) preparation of active component precursor solution
11.015g anhydrous cerium chloride, six chloride hydrate erbium of 4.679g and 3.139g ascorbic acid are weighed, 15.694g is added
Deionized water is placed in 60 DEG C of thermostat water baths stirring 60min and reaches 1000cP in clear shape and viscosity to solution, is lived
Property component precursor solution；
(2) co-catalyst presoma solion configures
Weigh six nitric hydrate yttrium of 5.655g, 4.358g eight is hydrated zirconium oxychloride, 6.860g manganese nitrate (50wt.%) solution
With 3.375g ascorbic acid, it is in that clarification is saturating that 16.873g deionized water, which is added, and is placed in 60 DEG C of thermostat water baths to stir 60min to solution
Bright shape and viscosity reaches 700cP, obtains co-catalyst presoma solion；
(3) preparation of catalyst carrier
It measures 5mL butyl titanate, the hydrochloric acid and 50mL deionized water that 10mL concentration is 2.5M, is placed in hydrothermal reaction kettle
In, it with 180 DEG C of hydro-thermal 2h, filtered, be dried in vacuo, obtained hydrochloric acid and optimize modified titanium dioxide sub-micron ball carrier, it is more
Secondary repeat the above steps total prepares carrier 100g.
(4) weighing for additive is formed
0.500g acetamide is weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 10%, 5%, 0.5%, and active component solution made from step (1) and step (2) is obtained
The mixing of co-catalyst presoma, stirs 20min, and step (3) load obtained is then added together with step (4) weighed additive
Body, stirring pugging are put in heat preservation and dryness 4h in 80 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 600 DEG C of roasting 1.5h in Muffle furnace in air atmosphere, sample is made
Product；
(7) catalytic activity is tested: catalytic activity test: 10mL catalyst sample being taken to be packed into catalyst performance evaluation reaction dress
In setting, quartzy bore is 10mm in evaluation response device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation
Are as follows: NO (600ppm), NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2
For carrier gas, catalyst grain size are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.
Denitration and de- dioxin efficiency minimum 97.8%, demercuration efficiency minimum 99.2% in 220-400 DEG C.
Comparative example 1
(1) preparation of active component precursor solution
11.015g anhydrous cerium chloride, six chloride hydrate erbium of 4.679g are weighed, 15.694g deionized water is added and is placed in 80 DEG C
It is in clear shape that thermostat water bath, which stirs 60min to solution, obtains active component precursor solution；
(2) co-catalyst presoma solion configures
Weigh six nitric hydrate yttrium of 5.655g, 4.358g eight is hydrated zirconium oxychloride and 6.860g manganese nitrate (50wt.%) is molten
Liquid, it is in clear shape that 16.873g deionized water, which is added, and is placed in 80 DEG C of thermostat water baths to stir 60min to solution, obtains helping and urge
Agent presoma solion；
(3) preparation of catalyst carrier
Weigh common commercial titanium dioxide (P25) 100g；
(4) weighing for additive is formed
0.500g acetamide is weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 10%, 5%, 0.5%, and active component solution made from step (1) and step (2) is obtained
The mixing of co-catalyst presoma, stirs 20min, and step (3) load obtained is then added together with step (4) weighed additive
Body, stirring pugging are put in heat preservation and dryness 4h in 80 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 500 DEG C of roasting 2h in Muffle furnace in air atmosphere, sample is made；
(7) catalytic activity is tested: NO (600ppm), NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,
7,8-TCDD(1ng TEQ/m3)、N2For carrier gas, catalyst grain size are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.Denitration efficiency is up to 95.0% in 220-400 DEG C, and de- dioxin efficiency is up to
74.5%, demercuration efficiency is up to 79.3%.
Comparative example 2:
(1) preparation of active component precursor solution
15.729g anhydrous cerium chloride is weighed, 15.729g deionized water is added and is placed in 80 DEG C of thermostat water bath stirring 80min
It is in clear shape to solution, obtains active component precursor solution；
(2) co-catalyst presoma solion configures
20.583g manganese nitrate (50wt.%) solution is weighed, addition 2.058g deionized water is placed in 50 DEG C of thermostat water baths and stirs
30min is mixed to solution in clear shape, obtains co-catalyst presoma solion；
(3) preparation of catalyst carrier
Weigh common commercial titanium dioxide (P25) 100g；
(4) weighing for additive is formed
0.500g carboxymethyl cellulose and 0.300g glycerine are weighed as molding additive；
It (5) is 100% meter, active component oxide, co-catalyst oxide and molding additive according to carrier quality
Three's mass percent is respectively 10%, 5%, 0.8%, and active component solution made from step (1) and step (2) is obtained
The mixing of co-catalyst presoma, stirs 20min, and step (3) load obtained is then added together with step (4) weighed additive
Body, stirring pugging are put in heat preservation and dryness 4h in 110 DEG C of air dry ovens after aging dry in the shade；
(6) roasting, molding of catalyst
Catalyst green body made from step (5) is placed in 600 DEG C of roasting 3h in Muffle furnace in air atmosphere, sample is made；
(7) catalytic activity is tested: catalytic activity test: 10mL catalyst sample being taken to be packed into catalyst performance evaluation reaction dress
In setting, quartzy bore is 10mm in evaluation response device, is passed through simulation gas and carries out activity rating.The composition of the gas of simulation
Are as follows: NO (600ppm), NH3(600ppm)、O2(6vol.%), Hg0(0.1mg/m3)、2,3,7,8-TCDD(1ng TEQ/m3)、N2
For carrier gas, catalyst grain size are as follows: diameter 3.5mm, long 3.5-5.5mm, GHSV 5000h-1, total gas flow rate 833mL/min.
350 DEG C or more denitration efficiencies are up to 89.5%, and 250 DEG C or less de- dioxin efficiency are up to take off in 68.7%, 220-400 DEG C
Mercury efficiency is up to 79.4%.
Claims (17)
1. a kind of denitration demercuration simultaneously takes off dioxin rare-earth base catalyst, it is characterised in that: the catalyst is with cerium oxide and oxidation
Erbium is catalytic active component, using zirconium oxide and/or yttrium oxide and/or manganese oxide as co-catalyst, optimizes modified metatitanic acid with hydrochloric acid
The titanium dioxide sub-micron ball that four butyl esters generate is carrier；In active component the mass ratio of cerium oxide and erbium oxide be 1:(0.01 ~
0.3)；
And the catalyst the preparation method is as follows:
(1) preparation of active component precursor solution:
Cerium salt, erbium salt and ascorbic acid are added in deionized water and are stirred to react under conditions of temperature is 50 ~ 60 DEG C
Reach 500-1000cP in clear shape and viscosity to solution, obtains solution A；
(2) co-catalyst presoma solion configures:
The condition that ascorbic acid and deionized water is added in zirconates and/or yttrium salt and/or manganese salt and is 50 ~ 60 DEG C in temperature
Under be stirred to react to solution in clear shape and viscosity reaches 500-1000cP, it is molten that co-catalyst presoma ion is made
Liquid B；
(3) it on the basis of carrier quality, is accounted for respectively by active component oxide, co-catalyst oxide and molding additive
The mass percent of carrier quality be 1 ~ 10%, 0.5 ~ 5% and 0.5 ~ 0.8%, by active component presoma made from step (1) from
It is excellent that hydrochloric acid is added together with molding additive after the mixing of co-catalyst presoma solion B made from sub- solution A and step (2)
To change in modified titanium dioxide sub-micron ball carrier, stirring pugging is put in heat preservation and dryness in air dry oven after aging,
Obtain catalyst green body；
(4) roasting of catalyst
Catalyst green body made from step (3) is placed in Muffle furnace to roast under oxidizing atmosphere and denitration demercuration de- two simultaneously are made
Dislike English rare-earth base catalyst；
Wherein: it is by four fourth of metatitanic acid that hydrochloric acid, which optimizes the preparation method of modified titanium dioxide sub-micron ball carrier, in step (3)
Ester, hydrochloric acid and water mixing are placed in hydrothermal reaction kettle, with 170 ~ 200 DEG C of hydro-thermal 2h, filtered, be dried in vacuo to obtain hydrochloric acid it is excellent
Change modified titanium dioxide sub-micron ball carrier；Wherein: concentration of hydrochloric acid is 2.5 M, butyl titanate: hydrochloric acid: deionized water
Volume ratio be 1:2:10；
Cerium salt described in step (1) is cerous nitrate or cerium chloride, and erbium salt is erbium nitrate or erbium chloride；Described in step (2)
Manganese salt is manganese nitrate, and zirconates is zirconium oxychloride, and yttrium salt is yttrium nitrate or yttrium chloride.
2. according to claim 1 while denitration demercuration takes off dioxin rare-earth base catalyst, it is characterised in that: cerium salt and erbium
The mixture of salt: ascorbic acid: the mass ratio of deionized water is 1:0.1 ~ 1:(1~10).
3. according to claim 2 while denitration demercuration takes off dioxin rare-earth base catalyst, it is characterised in that: cerium salt and erbium
The mixture of salt: ascorbic acid: the mass ratio of deionized water is 1:0.1 ~ 0.5:(1~5).
4. according to claim 1 while denitration demercuration takes off dioxin rare-earth base catalyst, it is characterised in that: zirconates and/
Or yttrium salt and/or manganese salt: ascorbic acid: the mass ratio of deionized water is 1:0.1 ~ 1:(1~10).
5. according to claim 4 while denitration demercuration takes off dioxin rare-earth base catalyst, it is characterised in that: zirconates and/
Or yttrium salt and/or manganese salt: ascorbic acid: the mass ratio of deionized water is 1:0.1 ~ 0.5:(1~5).
6. catalyst according to claim 1, it is characterised in that: molding additive described in step (3) is carboxylic propyl
One or more of methylcellulose, carboxymethyl cellulose, glycerine or acetamide.
7. catalyst according to claim 1, it is characterised in that: the drying temperature in step (3) is 80~110 DEG C, is done
The dry time is 2~4h；Maturing temperature in step (4) is 500~600 DEG C, and calcining time is 1.5~3h.
8. the preparation method that a kind of denitration demercuration simultaneously takes off dioxin rare-earth base catalyst, it is characterised in that: this method include with
Lower step:
(1) preparation of active component precursor solution
Cerium salt, erbium salt and ascorbic acid are added in deionized water and are stirred to react under conditions of temperature is 50 ~ 60 DEG C
Reach 500-1000cP in clear shape and viscosity to solution, obtains solution A；
(2) co-catalyst presoma solion configures
The condition that ascorbic acid and deionized water is added in zirconates and/or yttrium salt and/or manganese salt and is 50 ~ 60 DEG C in temperature
Under be stirred to react to solution in clear shape and viscosity reaches 500-1000cP, it is molten that co-catalyst presoma ion is made
Liquid B；
(3) it on the basis of carrier quality, is accounted for respectively by active component oxide, co-catalyst oxide and molding additive
The mass percent of carrier quality be 1 ~ 10%, 0.5 ~ 5% and 0.5 ~ 0.8%, by active component presoma made from step (1) from
It is excellent that hydrochloric acid is added together with molding additive after the mixing of co-catalyst presoma solion B made from sub- solution A and step (2)
To change in modified titanium dioxide sub-micron ball carrier, stirring pugging is put in heat preservation and dryness in air dry oven after aging,
Obtain catalyst green body；
(4) roasting of catalyst
Catalyst green body made from step (3) is placed in Muffle furnace to roast under oxidizing atmosphere and denitration demercuration de- two simultaneously are made
Dislike English rare-earth base catalyst；
It is by butyl titanate, salt that hydrochloric acid, which optimizes the preparation method of modified titanium dioxide sub-micron ball carrier, in step (3)
Acid and water mixing are placed in hydrothermal reaction kettle, with 170 ~ 200 DEG C of hydro-thermal 2h, are filtered, are dried in vacuo to obtain hydrochloric acid optimization and change
Titanium dioxide sub-micron ball carrier after property；Wherein: concentration of hydrochloric acid is 2.5 M, butyl titanate: hydrochloric acid: the body of deionized water
Product is than being 1:2:10；
Cerium salt described in step (1) is cerous nitrate or cerium chloride, and erbium salt is erbium nitrate or erbium chloride；Described in step (2)
Manganese salt is manganese nitrate, and zirconates is zirconium oxychloride, and yttrium salt is yttrium nitrate or yttrium chloride.
9. preparation method according to claim 8, it is characterised in that: the elemental mole ratios of cerium and erbium are 1 in active component:
(0.01~0.3)。
10. preparation method according to claim 8, it is characterised in that: the mixture of cerium salt and erbium salt: ascorbic acid: going
The mass ratio of ionized water is 1:0.1 ~ 1:(1~10).
11. preparation method according to claim 10, it is characterised in that: the mixture of cerium salt and erbium salt: ascorbic acid: going
The mass ratio of ionized water is 1:0.1 ~ 0.5:(1~5).
12. preparation method according to claim 8, it is characterised in that: zirconates and/or yttrium salt and/or manganese salt: Vitamin C
Acid: the mass ratio of deionized water is 1:0.1 ~ 1:(1~10).
13. preparation method according to claim 12, it is characterised in that: zirconates and/or yttrium salt and/or manganese salt: Vitamin C
Acid: the mass ratio of deionized water is 1:0.1 ~ 0.5:(1~5).
14. preparation method according to claim 8, it is characterised in that: molding additive described in step (3) is carboxylic third
One or more of ylmethyl cellulose, carboxymethyl cellulose, glycerine or acetamide.
15. preparation method according to claim 8, it is characterised in that: the drying temperature in step (3) is 80~110 DEG C,
Drying time is 2~4h.
16. preparation method according to claim 8, it is characterised in that: the maturing temperature in step (4) is 500~600
DEG C, calcining time is 1.5~3h.
17. denitration demercuration takes off the application in terms of dioxin to catalyst described in claim 1 at the same time.
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| CN111167475B (en) * | 2019-12-31 | 2022-08-09 | 南京环福新材料科技有限公司 | Catalyst for simultaneously denitrifying, removing mercury and removing dioxin and preparation method thereof |
| CN111330636B (en) * | 2020-02-21 | 2023-02-24 | 大唐南京环保科技有限责任公司 | Denitration, demercuration and dioxin removal catalyst and preparation method thereof |
| CN111760595A (en) * | 2020-07-08 | 2020-10-13 | 河南城建学院 | Be used for low temperature denitration to remove Hg0Of heteropoly acid/CeO2Base catalyst, preparation method and application thereof |
| CN111744501B (en) * | 2020-07-30 | 2023-02-03 | 南京工业大学 | Multifunctional environmental catalytic material for tail gas purification and preparation method and application thereof |
| CN111905721B (en) * | 2020-09-01 | 2022-09-13 | 天津大学 | Catalyst for low-temperature denitration and demercuration of titanium dioxide nano array and preparation method thereof |
| CN115501888B (en) * | 2022-10-21 | 2023-03-21 | 中科新天地（合肥）环保科技有限公司 | Efficient and synergistic denitration and dioxin removal catalyst and preparation method thereof |
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