CN115869989A - Preparation method of low-temperature denitration catalyst for tail gas of marine diesel engine - Google Patents
Preparation method of low-temperature denitration catalyst for tail gas of marine diesel engine Download PDFInfo
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- CN115869989A CN115869989A CN202211184172.XA CN202211184172A CN115869989A CN 115869989 A CN115869989 A CN 115869989A CN 202211184172 A CN202211184172 A CN 202211184172A CN 115869989 A CN115869989 A CN 115869989A
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- containing compound
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- tail gas
- diesel engine
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 239000000843 powder Substances 0.000 claims abstract description 52
- 238000001035 drying Methods 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 230000032683 aging Effects 0.000 claims abstract description 26
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 239000010937 tungsten Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 239000010955 niobium Substances 0.000 claims abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000006184 cosolvent Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000003301 Ceiba pentandra Nutrition 0.000 claims description 6
- 244000146553 Ceiba pentandra Species 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 6
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 4
- 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 4
- 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 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
- 229960000583 acetic acid Drugs 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 3
- 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 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004135 Bone phosphate Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 claims description 2
- LDPWMGUFXYRDRG-UHFFFAOYSA-I niobium(5+) pentaacetate Chemical compound [Nb+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LDPWMGUFXYRDRG-UHFFFAOYSA-I 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- 239000012778 molding material Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 33
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 24
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- 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 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- 239000011549 crystallization solution Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 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
- 238000007493 shaping process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine, in particular to a preparation process of the low-temperature denitration catalyst for the tail gas of the marine diesel engine, and belongs to the technical field of environmental catalysis. Firstly, tiO is added into a solution of vanadium-containing compound (molybdenum-containing compound + tungsten-containing compound) and other metal compound (niobium-containing compound + antimony-containing compound) with the mass ratio of 10 (2-4) to (1-3) to (3-5) 2 Performing low-temperature crystallization reaction on the powder to obtain catalyst powder, uniformly stirring the catalyst powder, a forming auxiliary material and water to form a mixture, mixing the mixture for more than one time to prepare pug, aging, filtering and extruding, primary drying and secondary drying, roasting and cooling to obtain a low-temperature denitration catalyst; the catalyst shows excellent low-temperature denitration performance, and the tail gas temperature of the marine low-speed diesel engine is lowerUnder the condition, the emission of nitrogen oxides in tail gas of the marine low-speed diesel engine can meet the requirements of the Tier III standard.
Description
Technical Field
The invention relates to a preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine, and belongs to the technical field of environmental catalysis.
Background
The flourishing development of international trade and fishery promotes the rapid development of the shipping industry in China, the emission of pollutants of marine diesel engines increasingly influences the environmental quality and the living health of residents, and great challenges are brought to the environmental air quality in coastal and coastal areas. With the effective control of the emission of the atmospheric pollutants of land fixed sources and mobile sources in China, the proportion of the atmospheric pollutants emitted by marine diesel engines is increasingly prominent. In order to deal with the severe situation of air pollution and effectively control the tail gas pollution of the marine diesel engine, in recent years, china successively sets up policies and standards related to the control of marine air pollutants. Internationally, according to MARPOL convention VI, 2016, 1, the implementation of the Tier III standard limits the discharge amount of nitrogen oxides of ships; from Tier II to Tier III, the NOx emission requirements are reduced from 14.4g/kWh to 3.4g/kWh. Therefore, with the successive issuing and implementation of various policies and standards, the development of the treatment of the nitrogen oxides in the tail gas of the ship is imperative.
Over the course of recent 40 years, vanadium-based catalyst systems have played an extremely important role in the catalytic purification of nitrogen oxides, both of stationary and mobile origin. Business V 2 O 5 -WO 3 (MoO 3 )/TiO 2 The catalyst has excellent NO at medium-high temperature section x Purification efficiency and SO resistance 2 Poisoning performance, the denitration catalyst of the system is mainly used in the denitration of the tail gas of the current marine diesel engine; however, for the vanadium-based catalyst used in practical applications, the operating temperature window is often in the higher temperature range of 300 ℃ to 425 ℃, and it is difficult to satisfy the NO requirement when the exhaust temperature is lower under the condition of cold start of the engine x Since the purification efficiency is required, research and development of a low-temperature denitration catalyst are attracting attention.
At present, the industrial extrusion molding process of the vanadium-based denitration catalyst generally comprises the steps of mixing, ageing, extruding, drying and roasting, and the active component solution is generally added in the mixing step. For example, patent application CN104815644A discloses a porous honeycomb denitration catalyst for ship denitration, a preparation method and an application thereof, wherein the denitration catalyst is a low-temperature vanadium-based denitration catalyst, and is prepared by adding titanium dioxide, stearic acid, deionized water, ammonia water, lactic acid, glass fiber, short fiber, ammonium metavanadate, ammonium metatungstate solution, hydroxypropyl methyl cellulose and polyethylene oxide into a mixing roll for 7 hours high-speed mixing, and then carrying out aging, extrusion, drying and roasting steps. However, since the addition of high content of ionic compounds such as V, mo, W, etc. during the mixing step results in too high viscosity of the slurry and makes the slurry difficult to extrude, it is necessary to improve the preparation method of the low temperature denitration catalyst, thereby improving the low temperature performance of the catalyst and avoiding the problem of difficulty in the molding process.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine, wherein the method comprises the steps of firstly loading an active component onto a carrier through a low-temperature crystallization reaction to obtain catalyst powder with high loading rate of the active component; then mixing and molding the catalyst powder, and then roasting at low temperature to obtain a low-temperature denitration catalyst; the catalyst is excellent in low-temperature denitration catalytic performance, and active components are added in a low-temperature crystallization step to replace the active components added in a mixing step in the prior art, so that the problems that the viscosity of pug is too high and the extrusion molding process is difficult are avoided.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine comprises the following steps:
(1) Preparation of catalyst powder
(a) Under the stirring state, dissolving a cosolvent A in water according to the mass ratio of 1-1 to 50, sequentially adding a vanadium-containing compound, a molybdenum-containing compound, a tungsten-containing compound and other metal compounds, heating to 85-98 ℃, obtaining a solution A after the solution is completely clarified and the color does not change any more, and continuing to keep the temperature and stir for later use;
under the stirring state, dispersing a niobium-containing compound and an antimony-containing compound in a cosolvent B, heating to 85-98 ℃, obtaining a solution B after the solution is completely clear and the color does not change any more, and continuing to keep the temperature and stir for later use;
dropwise adding the solution B into the solution A to form a solution C under the conditions of heat preservation and stirring at 85-98 ℃, and continuing to preserve heat and stir for later use;
the other metal compound is at least one of a copper-containing compound, a manganese-containing compound, a cerium-containing compound, a lanthanum-containing compound and a nickel-containing compound;
preferably, the other metal compound is a copper-containing compound, a manganese-containing compound, a cerium-containing compound, a lanthanum-containing compound, and a nickel-containing compound;
the cosolvent A is a monobasic, dibasic or tribasic organic acid; preferably, the cosolvent A is citric acid, oxalic acid or glacial acetic acid;
the cosolvent B is C1-C4 alcohols or C1-C4 ketones; preferably, the cosolvent B is ethanol or acetone;
the mass ratio of the vanadium-containing compound, the molybdenum-containing compound, the tungsten-containing compound, other metal compounds, the niobium-containing compound and the antimony-containing compound is as follows:
a vanadium-containing compound (molybdenum-containing compound and tungsten-containing compound), other metal compounds (niobium-containing compound and antimony-containing compound) =10, (2-4), (1-3) and (3-5);
wherein, the vanadium-containing compound is used as a main active ingredient; molybdenum-containing compounds, tungsten-containing compounds, niobium-containing compounds and antimony-containing compounds are used as main auxiliary agents; copper-containing compounds and manganese-containing compounds in other metal compounds are auxiliary active ingredients; cerium-containing compounds, lanthanum-containing compounds and nickel-containing compounds in other metal compounds are taken as auxiliary agents;
preferably, the mass ratio of the molybdenum-containing compound to the tungsten-containing compound is 1;
preferably, the vanadium-containing compound is ammonium metavanadate, vanadyl oxalate or vanadyl sulfate; the molybdenum-containing compound is ammonium molybdate or ammonium heptamolybdate; the tungsten-containing compound is ammonium metatungstate, ammonium paratungstate or ammonium tungstate; the copper-containing compound is copper sulfate, copper nitrate or cuprous acetate; the manganese-containing compound is manganese nitrate, manganese sulfate or manganese carbonate; the cerium-containing compound is cerium nitrate, cerium sulfate or cerium carbonate; the lanthanum-containing compound is lanthanum nitrate or lanthanum oxalate; the nickel-containing compound is nickel nitrate, nickel oxalate or nickel carbonate; the niobium-containing compound is niobium oxalate or niobium acetate; the antimony-containing compound is antimony acetate or antimony chloride;
(b) Mixing titanium dioxide (TiO) 2 ) Adding the powder into the solution C prepared in the step (a), stirring until the powder is uniformly dispersed, and aging to obtain a suspension D;
preferably, tiO 2 The mass ratio of the powder to the vanadium-containing compound in the solution C is 100-100;
preferably, the aging time is 12-24 h;
(c) Transferring the suspension D prepared in the step (b) into a hydrothermal kettle, reserving a space with the volume of 1/3-1/2 of the volume of the hydrothermal kettle, sealing the hydrothermal kettle, and then performing crystallization reaction at the crystallization temperature of 180-280 ℃ for 24-96 h; and after the crystallization reaction is finished, separating the solid, washing and drying to obtain the catalyst powder.
Preferably, the drying temperature is 100 ℃ to 120 ℃.
(2) Catalyst formation
Uniformly stirring catalyst powder, a forming auxiliary material and water to form a mixture, mixing the mixture to prepare pug, carrying out aging, filtering and squeezing, extruding, primary drying and secondary drying on the pug, roasting the pug at the low temperature of 420-650 ℃ for 28-42 h, and cooling to obtain a honeycomb-shaped low-temperature denitration catalyst for tail gas of a marine diesel engine;
the molding auxiliary material comprises kaolin, clay, ZSM-5 molecular sieve with the silicon-aluminum ratio (the molar ratio of silicon dioxide to aluminum oxide) of 15-40, hydroxymethyl cellulose, stearic acid, polyoxyethylene, glycerol, ammonia water, kapok and glass fiber.
Preferably, the mass ratio of the catalyst powder to the molding aid is 100 to 100.
Preferably, the mixing frequency is more than one time; the ageing temperature is 50-90 ℃, and the ageing time is 2-8 h; the primary drying temperature is 30-80 ℃, and the primary drying time is 250-400 h; the secondary drying temperature is 80-120 ℃, and the secondary drying time is 12-24 h; the mesh number of the die in the extrusion step is adjusted according to the particle size of the desired catalyst.
Advantageous effects
(1) The invention provides a preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine, which adopts a low-temperature crystallization method to load active components and an auxiliary agent on a carrier to obtain catalyst powder with high loading rate of the active components, wherein VO with low crystallinity is mainly contained in active component oxide (vanadium oxide cluster) in the catalyst powder 2 And V 2 O 3 And an auxiliary agent is added in the step of low-temperature crystallization, so that the dispersion degree and stability of the active component oxide loaded on the surface of the carrier are improved; because the active component ions are fully dispersed in the crystallization solution, the active component nanocluster growth time (namely the low-temperature crystallization reaction time) is long, the loading rate of the active components on the surface of the carrier is high, and the active components are uniformly dispersed, the mass fraction of the vanadium oxide clusters in the catalyst can reach 3% -6% according to the raw material ratio in the method, the catalyst in the mass fraction range shows good low-temperature denitration performance, and can be applied to tail gas denitration of a marine diesel engine, and the tail gas nitrogen oxide emission of the marine low-speed diesel engine can meet the requirements of the Tier III standard under the condition that the tail gas temperature of the marine low-speed diesel engine is low.
(2) The invention provides a preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine, which loads active components and an auxiliary agent on a carrier through low-temperature crystallization reaction to obtain catalyst powder in a prefabricating way.
(3) The invention provides a preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine, wherein an additive added in the method can be uniformly dispersed on the surface of the catalyst, so that the surface acidity of the catalyst is improved, the ammonia adsorption capacity is enhanced, and the low-temperature denitration performance of the catalyst is improved, and the hydrothermal stability of the catalyst can be enhanced to adapt to the change of different working conditions of the marine diesel engine.
(4) The invention provides a preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine, wherein the mass fraction of vanadium oxide clusters in the catalyst prepared by the method can reach 3-6%, and further research shows that the low-temperature denitration activity of the catalyst is optimal when the mass fraction of the vanadium oxide clusters is 4.1%; at 10000h -1 At the airspeed, more than 90 percent of NO can be achieved in a wide temperature window of 230-380 DEG C x Conversion, selective catalytic reduction of NO to ammonia x Has obvious effect, and the outlet keeps lower concentration of nitrogen oxide.
(5) The invention provides a preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine, which is characterized in that in the catalyst forming process, roasting is carried out for 28-42 h at the temperature of 420-650 ℃, low-temperature crystallization embedding and a lower roasting temperature range can enable low-valence vanadium oxide to be incompletely oxidized, and more V is reserved in an active component cluster 4+ Improve V 4+ /V 5+ The ratio provides more oxidation-reduction active pairs, thereby improving the low-temperature denitration performance of the catalyst.
Detailed Description
The invention will be described in more detail with reference to specific examples, which should not be construed as limiting the scope of the invention.
The process is conventional unless otherwise specified, and the starting materials are commercially available from a public source.
ZSM-5 molecular sieves were obtained from Tianjin Shenneng technology, inc. at the silica to alumina ratio (SiO) of the molecular sieves 2 And Al 2 O 3 The amount of the substance(s) of (a) is 15 to 40.
The following comparative examples and examples:
evaluation of catalyst Activity: intercepting a low-temperature denitration catalyst with the length multiplied by the width multiplied by the height multiplied by 30mm multiplied by 60mm, wherein the reaction temperature is 180-400 ℃, and the gas condition is that the tail gas of a simulated marine diesel engine (1000 ppm NH) 3 +1000ppmNO+100ppm SO 2 +3wt.％H 2 O+15wt.％O 2 )，N 2 Is balanced gas, the pressure is normal pressure, and the space velocity is 10000h -1 The reaction activity of the catalyst is evaluated by the conversion rate of NO, and the concentration N of nitrogen oxides in the tail gas of the marine diesel engine is simulated before denitration 0 (unit is ppm) and simulation of marine diesel engine tail gas NO after denitration x The concentration N (in ppm) was analyzed by using a model CLD60 nitrogen oxide analyzer manufactured by ECO Physics of Switzerland;
NO x conversion (%) calculation formula: NO x conversion＝(N 0 -N)/N 0 ×100％。
Example 1
A preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine comprises the following specific steps:
(1) Preparation of catalyst powder
(a) Under the stirring state, 5 g of citric acid is dissolved in 250 g of distilled water according to the mass ratio of 1;
under the stirring state, 0.2 g of niobium oxalate and 0.2 g of antimony acetate are dispersed in 30mL of acetone, the mixture is heated to 90 ℃, a solution B is obtained after the solution is completely clear and the color does not change any more, and the heat preservation and the stirring are continued for standby application;
dropwise adding the solution B into the solution A under the conditions of heat preservation and stirring at 90 ℃ to form a solution C, and continuously preserving heat and stirring for later use; wherein the mass ratio of ammonium metavanadate (ammonium heptamolybdate + ammonium metatungstate) to (copper nitrate + manganese nitrate + cerium nitrate + lanthanum nitrate + nickel nitrate) to (niobium oxalate + antimony acetate) is 10;
(b) 20 g of TiO 2 Adding the powder into the solution C prepared in the step (a), and adding TiO 2 The mass ratio of the powder to the vanadium-containing compound in the solution C is 100;
(c) Transferring the suspension D prepared in the step (b) into a hydrothermal kettle, and sealing the hydrothermal kettle in an oven for crystallization at 210 ℃ for 48 hours after a space with the volume of 1/3 of that of the hydrothermal kettle is reserved in the hydrothermal kettle; and filtering the crystallized suspension D, cleaning the obtained solid, and drying in an oven at 100 ℃ to obtain the catalyst powder.
(2) Catalyst formation
Mixing 4000 g of catalyst powder, 600 g of forming auxiliary material and 3200 g of deionized water, wherein the mass ratio of the catalyst powder to the forming auxiliary material is 100; the mud material is subjected to ageing, filtering and squeezing by a 46-mesh die, extruding, primary drying and secondary drying, then is roasted for 28 hours at the temperature of 520 ℃, and is naturally cooled to obtain the low-temperature denitration catalyst for the tail gas of the marine diesel engine;
the molding auxiliary materials are 120 g of kaolin, 100 g of clay, 100 g of ZSM-5 molecular sieve, 15 g of hydroxymethyl cellulose, 10 g of stearic acid, 30 g of polyethylene oxide, 5 g of glycerol, 100 g of ammonia water, 20 g of kapok and 100 g of glass fiber; wherein the ageing temperature is 60 ℃, and the ageing time is 8 hours; the primary drying temperature is 60 ℃, and the primary drying time is 250h; the secondary drying temperature is 100 ℃, and the drying time is 12h.
Example 2
Example 2 based on example 1 only, "(b) 20 g TiO in step (1) 2 Powder "replace" (b) 15 g TiO 2 Powder ", tiO 2 The mass ratio of the powder to the vanadium-containing compound in the solution C is 15:1; and other conditions are unchanged, so that the low-temperature denitration catalyst for the tail gas of the marine diesel engine is obtained.
Example 3
Example 3 based on example 1 only, "(b) 20 g TiO in step (1) 2 Powder "replace" (b) 10 g TiO 2 Powder ", tiO 2 The mass ratio of the powder to the vanadium-containing compound in the solution C is 10:1; and other conditions are unchanged, so that the low-temperature denitration catalyst for the tail gas of the marine diesel engine is obtained.
Example 4
A preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine comprises the following specific steps:
(1) Preparation of catalyst powder
(a) Under the stirring state, 5 g of oxalic acid is dissolved in distilled water according to the mass ratio of 1;
under the stirring state, 0.25 g of niobium oxalate and 0.25 g of antimony acetate are dispersed in 30mL of ethanol, the solution is heated to 85 ℃, a solution B is obtained after the solution is completely clear and the color does not change any more, and the solution B is kept at the temperature and is stirred for standby application;
slowly dripping the solution B into the solution A under the conditions of heat preservation and stirring at 85 ℃ to form a solution C, and continuing to preserve heat and stir for later use; wherein the mass ratio of ammonium metavanadate (ammonium molybdate + ammonium tungstate) to (copper sulfate + manganese sulfate + cerium sulfate + lanthanum nitrate + nickel oxalate) to (niobium oxalate + antimony acetate) is 10:2:3:5;
(b) Mixing 15 g of TiO 2 Adding the powder into the solution C prepared in the step (a), and adding TiO 2 The mass ratio of the powder to the vanadium-containing compound in the solution C is 15:1; stirring, dispersing and aging for 24h to obtain a suspension D;
(c) Transferring the suspension D prepared in the step (b) into a hydrothermal kettle, sealing the hydrothermal kettle and placing the hydrothermal kettle in an oven for crystallization at 180 ℃ for 96 hours after a space with the volume of 1/2 of the volume of the hydrothermal kettle is reserved in the hydrothermal kettle; and filtering the crystallized solution D, cleaning the obtained solid, and drying in a 120 ℃ drying oven to obtain the catalyst powder.
(2) Catalyst shaping
Mixing 4000 g of catalyst powder, 600 g of forming auxiliary material and 3200 g of deionized water, wherein the mass ratio of the catalyst powder to the forming auxiliary material is 100;
the molding auxiliary materials are 120 g of kaolin, 100 g of clay, 100 g of ZSM-5 molecular sieve, 15 g of hydroxymethyl cellulose, 10 g of stearic acid, 30 g of polyethylene oxide, 5 g of glycerol, 100 g of ammonia water, 20 g of kapok and 100 g of glass fiber; wherein the ageing temperature is 50 ℃, and the ageing time is 8 hours; the primary drying temperature is 80 ℃, and the primary drying time is 250h; the secondary drying temperature is 120 ℃, and the drying time is 12h.
Example 5
A preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine comprises the following specific steps:
(1) Preparation of catalyst powder
(a) Under the stirring state, dissolving 5 g of glacial acetic acid in distilled water according to the mass ratio of 1;
under the stirring state, dispersing 0.15 g of niobium oxalate and 0.15 g of antimony chloride in 30mL of acetone, heating to 98 ℃, obtaining a solution B after the solution is completely clear and the color does not change any more, and continuing to keep the temperature and stir for later use;
slowly dripping the solution B into the solution A under the conditions of heat preservation and stirring at 98 ℃ to form a solution C, and continuing to preserve heat and stir for later use; wherein, the mass ratio of (ammonium heptamolybdate + ammonium paratungstate) to (cuprous sulfate + manganese carbonate + cerium carbonate + lanthanum nitrate + nickel carbonate) to (niobium oxalate + antimony chloride) is 10:4:1:3;
(b) Adding 15 g of TiO 2 Adding the powder into the solution C prepared in the step (a), stirring and dispersing, and aging for 24 hours to obtain a suspension D;
(c) Transferring the suspension D prepared in the step (b) into a hydrothermal kettle, and sealing the hydrothermal kettle in an oven for crystallization at 280 ℃ for 24 hours after a space with the volume of 1/2 of that of the hydrothermal kettle is reserved in the hydrothermal kettle; and filtering the crystallized solution D, cleaning the obtained solid, and drying in an oven at 100 ℃ to obtain the catalyst powder.
(2) Catalyst formation
Mixing 4000 g of catalyst powder, 800 g of forming auxiliary material and 2800 g of deionized water, wherein the mass ratio of the catalyst powder to the forming auxiliary material is 100;
the molding auxiliary material comprises 120 g of kaolin, 100 g of clay, 100 g of ZSM-5 molecular sieve, 15 g of hydroxymethyl cellulose, 10 g of stearic acid, 30 g of polyethylene oxide, 5 g of glycerol, 100 g of ammonia water, 20 g of kapok and 100 g of glass fiber; wherein the ageing temperature is 90 ℃, and the ageing time is 2 hours; the primary drying temperature is 30 ℃, and the primary drying time is 400 hours; the secondary drying temperature is 80 ℃, and the drying time is 24h.
Comparative example 1
A method for preparing a low-temperature denitration catalyst for tail gas of a marine diesel engine by using an impregnation method comprises the following specific steps:
(1) Preparation of catalyst powder
(a) Dissolving 5 g of citric acid in distilled water according to a mass ratio of 1;
under the stirring state, 0.2 g of niobium oxalate and 0.2 g of antimony acetate are dispersed in acetone, heated to 90 ℃, and solution B is obtained after the solution is completely clear and the color does not change any more, and the solution B is continuously stirred at the constant temperature for standby;
slowly dripping the solution B into the solution A under the conditions of heat preservation and stirring at 90 ℃ to form a solution C, and continuing to preserve heat and stir for later use; (ii) a Wherein the mass ratio of ammonium metavanadate (ammonium heptamolybdate and ammonium metatungstate) to (copper nitrate, manganese nitrate, cerium nitrate, lanthanum nitrate and nickel nitrate) to (niobium oxalate and antimony acetate) is 10:3:2:4;
(b) Mixing 15 g of TiO 2 Adding the powder into the solution C prepared in the step (a), stirring and dispersing, and aging for 12 hours to obtain a suspension D;
(c) Stirring the suspension D at the constant temperature of 80 ℃ for dewatering for 10 hours;
(d) Washing the mixture obtained in the step (c) after constant-temperature stirring and water removal for three times by using secondary distilled water, and keeping the temperature at 80 ℃ for 48 hours;
(e) And (d) roasting the mixture dried at constant temperature in the step (d) at 400 ℃ for 4h to obtain the catalyst powder.
(2) Catalyst formation
Mixing 4000 g of catalyst powder, 600 g of forming auxiliary material and 3200 g of deionized water, wherein the mass ratio of the catalyst powder to the forming auxiliary material is 100;
the molding auxiliary materials are 120 g of kaolin, 100 g of clay, 100 g of ZSM-5 molecular sieve, 15 g of hydroxymethyl cellulose, 10 g of stearic acid, 30 g of polyethylene oxide, 5 g of glycerol, 100 g of ammonia water, 20 g of kapok and 100 g of glass fiber; wherein the ageing temperature is 60 ℃, and the ageing time is 8 hours; the primary drying temperature is 60 ℃, and the primary drying time is 250h; the secondary drying temperature is 100 ℃, and the drying time is 12h.
The low-temperature denitration catalysts for tail gas of marine diesel engines, prepared in examples 1 to 5 and comparative example 1, were evaluated for activity at 180 to 440 ℃, and the results are shown in table 1:
TABLE 1 NO at different temperatures for catalysts prepared in examples 1-5 and comparative example 1 x Conversion rate
As can be seen from table 1:
(1) According to the catalystThe raw material ratio of each component is calculated, the mass fraction of the vanadium oxide cluster in the catalyst can reach 3% -6%, and the vanadium oxide cluster with the mass fraction can give consideration to the loading rate and the dispersion degree of an active component oxide carrier, so that the catalyst shows good low-temperature denitration catalytic performance; when the mass fraction of vanadium oxide clusters in the catalyst is 3.2-4.1%, the low-temperature denitration catalyst is used for catalytically reducing NO x The conversion rate of (a) increases as the mass fraction of the vanadium oxide cluster supported in the catalyst increases; when the mass fraction of the vanadium oxide cluster reaches 4.1%, the catalytic performance is optimal; when the mass fraction of vanadium oxide clusters in the catalyst continues to increase, the catalytic performance is obviously reduced (4.1-4.3%), and then slowly increased (4.3-5.9%), but the catalytic performance is still lower than that of the catalyst when the mass fraction of vanadium oxide clusters reaches 4.1%.
(2) As can be seen from comparison of example 2 with comparative example 1, in the case where the mass fraction of vanadium oxide clusters is the same, the "crystallization reaction" in step (c) is replaced by the "impregnation method" to obtain a catalyst powder for the catalytic reduction of NO x The conversion rate of (a) is reduced; therefore, in the preparation method provided by the invention, the crystallization process of the active component and the auxiliary agent on the surface of the carrier is more favorable for uniformly dispersing the active component, so that the catalytic activity is improved.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (9)
1. A preparation method of a low-temperature denitration catalyst for tail gas of a marine diesel engine is characterized by comprising the following steps: the method comprises the following steps:
(a) Under the stirring state, dissolving a cosolvent A in water according to the mass ratio of 1-1 to 50, sequentially adding a vanadium-containing compound, a molybdenum-containing compound, a tungsten-containing compound and other metal compounds, heating to 85-98 ℃, and obtaining a solution A after the solution is completely clarified and the color does not change any more;
under the stirring state, dispersing a niobium-containing compound and an antimony-containing compound in a cosolvent B, heating to 85-98 ℃, and obtaining a solution B after the solution is completely clear and the color is not changed any more;
dropwise adding the solution B into the solution A at 85-98 ℃ under the condition of stirring to form a solution C;
the other metal compound is at least one of a copper-containing compound, a manganese-containing compound, a cerium-containing compound, a lanthanum-containing compound and a nickel-containing compound;
the cosolvent A is a monobasic, dibasic or tribasic organic acid;
the cosolvent B is C1-C4 alcohol or C1-C4 ketone;
the vanadium-containing compound (molybdenum-containing compound + tungsten-containing compound) and other metal compounds (niobium-containing compound + antimony-containing compound) are mixed according to the mass ratio of 10 (2-4) to (1-3) to (3-5);
(b) Adding TiO into the mixture 2 Adding the powder into the solution C, stirring until the powder is uniformly dispersed, and aging to obtain a suspension D;
(c) And transferring the suspension D into a hydrothermal kettle, sealing, performing crystallization reaction at 180-280 ℃ for 24-96 h, separating the solid, washing and drying to obtain the catalyst powder.
2. The preparation method of the low-temperature denitration catalyst for the tail gas of the marine diesel engine according to claim 1, characterized by comprising the following steps:
the cosolvent A is citric acid, oxalic acid or glacial acetic acid; the cosolvent B is ethanol or acetone;
the vanadium-containing compound is ammonium metavanadate, vanadyl oxalate or vanadyl sulfate; the molybdenum-containing compound is ammonium molybdate or ammonium heptamolybdate; the tungsten-containing compound is ammonium metatungstate, ammonium paratungstate or ammonium tungstate; the copper-containing compound is copper sulfate, copper nitrate or cuprous acetate; the manganese-containing compound is manganese nitrate, manganese sulfate or manganese carbonate; the cerium-containing compound is cerium nitrate, cerium sulfate or cerium carbonate; the lanthanum-containing compound is lanthanum nitrate or lanthanum oxalate; the nickel-containing compound is nickel nitrate, nickel oxalate or nickel carbonate; the niobium-containing compound is niobium oxalate or niobium acetate; the antimony-containing compound is antimony acetate or antimony chloride.
3. The preparation method of the low-temperature denitration catalyst for the tail gas of the marine diesel engine according to claim 1, characterized by comprising the following steps: the other metal compounds are copper-containing compounds, manganese-containing compounds, cerium-containing compounds, lanthanum-containing compounds and nickel-containing compounds; the mass ratio of the molybdenum-containing compound to the tungsten-containing compound is 1.
4. The preparation method of the low-temperature denitration catalyst for the tail gas of the marine diesel engine according to claim 1, which is characterized by comprising the following steps: the TiO is 2 The mass ratio of the powder to the vanadium-containing compound in the solution C is (100); the aging time is 12-24 h.
5. The preparation method of the low-temperature denitration catalyst for the tail gas of the marine diesel engine according to claim 1, characterized by comprising the following steps: the drying temperature is 100-120 ℃.
6. The preparation method of the low-temperature denitration catalyst for the tail gas of the marine diesel engine according to claim 2, characterized by comprising the following steps: the other metal compounds are copper-containing compounds, manganese-containing compounds, cerium-containing compounds, lanthanum-containing compounds and nickel-containing compounds; the mass ratio of the molybdenum-containing compound to the tungsten-containing compound is 1; the TiO is 2 The mass ratio of the powder to the vanadium-containing compound in the solution C is (100); the aging time is 12-24 h; the drying temperature is 100-120 ℃.
7. The preparation method of the low-temperature denitration catalyst for the tail gas of the marine diesel engine according to any one of claims 1 to 6, characterized by comprising the following steps: the method also comprises the step of forming the catalyst, and the steps are as follows:
uniformly stirring the catalyst powder, a forming auxiliary material and water to form a mixture, mixing the mixture to prepare pug, carrying out aging, filtering and squeezing, extruding, primary drying and secondary drying on the pug, roasting the pug at the low temperature of 420-650 ℃ for 28-42 h, and cooling to obtain the low-temperature denitration catalyst for the tail gas of the marine diesel engine;
the auxiliary molding material comprises kaolin, clay, ZSM-5 molecular sieve with the silica-alumina ratio of 15-40, hydroxymethyl cellulose, stearic acid, polyoxyethylene, glycerol, ammonia water, kapok and glass fiber.
8. The preparation method of the low-temperature denitration catalyst for the tail gas of the marine diesel engine according to claim 7, characterized by comprising the following steps: the mass ratio of the catalyst powder to the molding auxiliary material is 100-100, and the mass ratio of the catalyst powder to water is 100.
9. The preparation method of the low-temperature denitration catalyst for the tail gas of the marine diesel engine according to claim 7, characterized by comprising the following steps: the mixing frequency is more than one time; the ageing temperature is 50-90 ℃, and the ageing time is 2-8 h; the primary drying temperature is 30-80 ℃, and the primary drying time is 250-400 h; the secondary drying temperature is 80-120 ℃, and the secondary drying time is 12-24 h.
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