CN114682250A - Ceramic fiber filter tube catalyst and stepwise preparation method thereof - Google Patents
Ceramic fiber filter tube catalyst and stepwise preparation method thereof Download PDFInfo
- Publication number
- CN114682250A CN114682250A CN202011589817.9A CN202011589817A CN114682250A CN 114682250 A CN114682250 A CN 114682250A CN 202011589817 A CN202011589817 A CN 202011589817A CN 114682250 A CN114682250 A CN 114682250A
- Authority
- CN
- China
- Prior art keywords
- fiber filter
- ceramic fiber
- filter tube
- source
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 223
- 239000000835 fiber Substances 0.000 title claims abstract description 208
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000010936 titanium Substances 0.000 claims abstract description 79
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 79
- 238000001035 drying Methods 0.000 claims abstract description 57
- 239000004094 surface-active agent Substances 0.000 claims abstract description 42
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000011572 manganese Substances 0.000 claims abstract description 28
- 238000005470 impregnation Methods 0.000 claims abstract description 27
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 144
- 239000002245 particle Substances 0.000 claims description 94
- 239000004408 titanium dioxide Substances 0.000 claims description 61
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 60
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 19
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 19
- 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 14
- 239000002253 acid Substances 0.000 claims description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 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 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- -1 polysiloxane Polymers 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- FUECGUJHEQQIFK-UHFFFAOYSA-N [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] FUECGUJHEQQIFK-UHFFFAOYSA-N 0.000 claims description 2
- GJAROXYKDRBDBI-UHFFFAOYSA-J [W+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [W+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJAROXYKDRBDBI-UHFFFAOYSA-J 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 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
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 229940099596 manganese sulfate Drugs 0.000 claims 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003546 flue gas Substances 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 11
- 238000002791 soaking Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 8
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 8
- 229910001930 tungsten oxide Inorganic materials 0.000 description 8
- 238000004506 ultrasonic cleaning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
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- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- 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
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Abstract
The invention relates to the field of flue gas denitration, and discloses a ceramic fiber filter tube catalyst and a stepwise preparation method thereof, wherein the method comprises the following steps: (1) carrying out first impregnation on the ceramic fiber filter tube by adopting an inorganic titanium source solution, and obtaining a first ceramic fiber filter tube through first drying and first roasting; (2) carrying out second impregnation on the first ceramic fiber filter tube by adopting a surfactant solution, and carrying out second drying to obtain a modified ceramic fiber filter tube; (3) carrying out third impregnation on the modified ceramic fiber filter tube by adopting an organic titanium source solution, and carrying out third drying and second roasting to obtain a second ceramic fiber filter tube; (4) and (3) carrying out fourth impregnation on the second ceramic fiber filter tube by adopting a solution containing a manganese source and/or a vanadium source and an M source, and carrying out fourth drying and third roasting to obtain the ceramic fiber filter tube catalyst. The ceramic tube matrix and the denitration catalyst in the ceramic fiber filter tube catalyst provided by the invention are firmly combined, the active components are not easy to fall off and are uniformly dispersed, and the denitration activity is better.
Description
Technical Field
The invention relates to the field of flue gas denitration, and particularly relates to a ceramic fiber filter tube catalyst and a stepwise preparation method thereof.
Background
China is a country with an energy structure mainly based on fire coal, pollutants generated by the fire coal mainly comprise dust, sulfur dioxide, nitrogen oxides and the like, and the national emission standard of the pollutants is stricter. The flue gas purification system is generally formed by combining and connecting a flue gas SCR denitration system, a dedusting system and a desulfurization system in series, and has the defects of large occupied area, high operation and maintenance cost, mutual interference among the systems and the like. The ceramic fiber filter tube catalyst can realize the effect of synergistic removal of particulate matters, sulfur dioxide and nitrogen oxides in flue gas, and has the advantages of small occupied area and low operation cost. However, the following problems still remain: (1) the ceramic tube substrate and the denitration catalyst are not firmly combined, and active components are easy to fall off after passing through flue gas or in a back blowing process; (2) the catalyst active components are not uniformly dispersed, which easily causes poor catalyst activity of the ceramic tube.
Therefore, the ceramic fiber filter tube catalyst and the stepwise preparation method thereof have important significance.
Disclosure of Invention
The invention aims to solve the problems that the combination of a ceramic tube substrate and a denitration catalyst is not firm and the prepared ceramic tube catalyst has poor denitration activity in the prior art, and provides a ceramic fiber filter tube catalyst and a stepwise preparation method thereof, wherein the method can ensure that the combination of the ceramic tube substrate and the denitration catalyst is firm and active components are not easy to fall off; and the active components of the catalyst are uniformly dispersed, so that the denitration activity of the ceramic tube catalyst is improved.
In order to achieve the above object, a first aspect of the present invention provides a stepwise preparation method of a ceramic fiber filter tube catalyst, the method comprising:
(1) carrying out first impregnation on the ceramic fiber filter tube by using a solution containing an inorganic titanium source, and then carrying out first drying and first roasting to obtain a first ceramic fiber filter tube loaded with large-particle titanium dioxide;
(2) carrying out second impregnation on the first ceramic fiber filter tube by using a solution containing a surfactant, and then carrying out second drying to obtain a modified ceramic fiber filter tube;
(3) carrying out third impregnation on the modified ceramic fiber filter tube by adopting a solution containing an organic titanium source, and then carrying out third drying and second roasting to obtain a second ceramic fiber filter tube loaded with large-particle titanium dioxide and small-particle titanium dioxide;
(4) carrying out fourth impregnation on the second ceramic fiber filter tube by adopting a solution containing a manganese source and/or a vanadium source and an M source, and then carrying out fourth drying and third roasting to obtain a ceramic fiber filter tube catalyst;
wherein M is at least one of Mo, W, Ce, Fe, Nb, Ni and Co. The second aspect of the invention provides a ceramic fiber filter tube catalyst prepared by the method of the first aspect of the invention, based on the total amount of the ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 74-82 wt%, the content of titanium dioxide is 12-18 wt%, and the content of active components is 6-14 wt% calculated by oxides, wherein the active components comprise Mn and/or V and Mo, W, Ce, Fe, Nb, Ni and CoAt least one of (a); the specific surface area of the catalyst is 110-300m2The pore volume of the catalyst is 0.1-0.4cm3/g。
According to the technical scheme, the ceramic fiber filter tube loaded with titanium dioxide particles with the sizes of 30-50nm and 5-20nm is obtained by sequentially dipping inorganic titanium, the surfactant and organic titanium in the ceramic fiber filter tube, and then the active component is loaded, so that the ceramic tube substrate and the denitration catalyst are combined more firmly, the active component is not easy to fall off, and the catalyst has larger specific surface area and pore volume; and the active components of the catalyst are uniformly dispersed, so that the denitration activity of the ceramic fiber filter tube catalyst is improved. For example, the powder removal rate of the ceramic fiber filter tube catalyst prepared in example 1 of the present invention was 0.5%, and when the catalyst was used in a denitration reaction, the denitration efficiencies at 200 ℃, 250 ℃, 300 ℃ and 350 ℃ were 93%, 95%, 97% and 98%, respectively; while the powder removal rate of the catalyst prepared in comparative example 1 was 8%, when the catalyst was used in the denitration reaction, the denitration efficiencies at 200 ℃, 250 ℃, 300 ℃ and 350 ℃ were 82%, 85% and 86%, respectively, under the same conditions.
Drawings
FIG. 1 is an SEM photograph of a second ceramic fiber filter tube prepared in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
At present, the method for preparing the ceramic fiber filter tube catalyst generally adopts inorganic titanium and/or organic titanium as a precursor, the ceramic fiber filter tube is repeatedly impregnated for a plurality of times, and then the loading of active components is carried out. In order to solve the above problems, the inventors of the present invention have found in their studies that titanium dioxide particles having a large particle diameter (30 to 50nm) are formed in the pores of a ceramic fiber filter tube by first using inorganic titanium as a precursor; then modifying the surface of the titanium dioxide particles by using a surfactant; finally, titanium dioxide particles with smaller particle size (5-20nm) are formed in situ by using organic titanium as a precursor under the action of a surfactant, the surfactant is used for modifying the outer surface of large particles, reducing the surface tension, facilitating organic titanium dispersion to enter gaps of the large particles and providing reaction sites for the formation of small organic titanium particles, so that the particles with smaller particle size are formed. Under the action of a surfactant, inorganic titanium and organic titanium are sequentially adopted to impregnate a ceramic fiber filter tube step by step, small-particle titanium dioxide can be filled in gaps of large-particle titanium dioxide, large particles and small particles are connected together to form a titanium dioxide layer which is more firmly combined with the ceramic fiber filter tube, and then active components are loaded to prepare the ceramic fiber filter tube catalyst, wherein the ceramic fiber filter tube catalyst is not easy to fall off when smoke is filtered and back blowing is carried out; meanwhile, the specific surface area and the pore volume of the catalyst are improved due to the formation of small particles, so that the uniform dispersion of active components of the catalyst is facilitated, and the denitration activity of the ceramic fiber filter tube catalyst is further improved.
As previously mentioned, a first aspect of the present invention provides a stepwise method of preparing a ceramic fiber filter tube catalyst, the method comprising:
(1) carrying out first impregnation on the ceramic fiber filter tube by using a solution containing an inorganic titanium source, and then carrying out first drying and first roasting to obtain a first ceramic fiber filter tube loaded with large-particle titanium dioxide;
(2) carrying out second impregnation on the first ceramic fiber filter tube by using a solution containing a surfactant, and then carrying out second drying to obtain a modified ceramic fiber filter tube;
(3) carrying out third impregnation on the modified ceramic fiber filter tube by adopting a solution containing an organic titanium source, and then carrying out third drying and second roasting to obtain a second ceramic fiber filter tube loaded with large-particle titanium dioxide and small-particle titanium dioxide;
(4) carrying out fourth impregnation on the second ceramic fiber filter tube by adopting a solution containing a manganese source and/or a vanadium source and an M source, and then carrying out fourth drying and third roasting to obtain a ceramic fiber filter tube catalyst;
wherein M is at least one of Mo, W, Ce, Fe, Nb, Ni and Co.
The method for preparing the ceramic fiber filter tube catalyst can be summarized as sequentially loading inorganic titanium, a surfactant and organic titanium on a ceramic fiber filter tube, namely sequentially adopting the inorganic titanium and the organic titanium to carry out stepwise impregnation on the ceramic fiber filter tube under the action of the surfactant, and then carrying out loading on active components; in the prior art, the ceramic fiber filter tube is usually repeatedly impregnated for many times by adopting inorganic titanium or organic titanium or a mode of mixing inorganic titanium and organic titanium, and then the active component is loaded, and the method does not comprise the step of modifying by adopting a surfactant and the step of impregnating step by step.
In some embodiments of the present invention, it is preferable that the large particle titanium dioxide has a particle size of 30 to 50nm and the small particle titanium dioxide has a particle size of 5 to 20 nm. In the invention, the small-particle titanium dioxide can be filled in gaps of large-particle titanium dioxide, so that the large particles and the small particles are connected together to form a titanium dioxide layer which is firmly combined with the ceramic fiber filter tube, and thus, active components of the catalyst are not easy to fall off after passing through smoke or in a back blowing process.
In some embodiments of the present invention, there is no particular limitation on the ceramic fiber filter tube in step (1), and a ceramic fiber filter tube existing in the art may be used, and preferably, the ceramic fiber filter tube is made of the following two materials: one is a ceramic fiber filter tube which is formed by coating or winding a ceramic fiber composite membrane on the surface of tubular porous cordierite ceramic, tubular porous mullite ceramic or tubular porous silicon carbide ceramic; the other is a ceramic fiber filter tube formed by aluminum silicate fibers.
In some embodiments of the present invention, the amount of the inorganic titanium source-containing solution in step (1) is not particularly limited as long as the first ceramic fiber filter tube loaded with large-particle titanium dioxide can be obtained, and preferably, the volume ratio of the inorganic titanium source-containing solution to the ceramic fiber filter tube is 1 to 20: 1, more preferably 1 to 12: 1.
in some embodiments of the present invention, the concentration of the inorganic titanium source solution in step (1) is selected from a wide range, preferably as TiO2The concentration of the solution containing the inorganic titanium source is 5-20 wt%.
The invention is not particularly limited as long as the solution containing the inorganic titanium source in the step (1) is formed by mixing the inorganic titanium source and the solvent, and TiO can be formed25-20 wt% of the solution. The solvent used for forming the solution containing the inorganic titanium source in the step (1) is not particularly limited in the present invention, and is preferably water, more preferably deionized water, in view of saving the production cost. The mixing according to the invention can be carried out under stirring.
In some embodiments of the present invention, the inorganic titanium source is selected from a wide range in step (1), and preferably, the inorganic titanium source is selected from at least one of titanium sulfate, metatitanic acid and titanium tetrachloride, and more preferably, titanium sulfate. In this preferred case, it is more advantageous to obtain the first ceramic fiber cartridge loaded with large-particle titanium dioxide having a particle size of 30 to 50 nm.
In some embodiments of the present invention, the amount of the solution containing the surface modifier in step (2) is not particularly limited as long as the modification of the surface of the large-particle titanium dioxide, the reduction of the surface tension, and the facilitation of the penetration of the organic titanium dispersion into the gaps between the large particles can be achieved, and preferably, the volume ratio of the solution containing the surfactant to the first ceramic fiber filter tube is 1 to 20: 1, more preferably 1 to 15: 1.
in some embodiments of the present invention, the concentration of the surfactant-containing solution in step (2) is selected from a wide range, preferably the concentration of the surfactant-containing solution is 1 to 5 wt%, more preferably 2 to 4 wt%.
The present invention is not particularly limited to the mixing of a surfactant with a solvent to form the surfactant-containing solution of step (2), as long as a uniform and stable solution having a concentration of 1 to 5% by weight can be formed. The solvent is not particularly limited in the present invention, and is preferably water, and more preferably deionized water, in order to reduce the cost. The mixing according to the invention can be carried out under stirring.
In some embodiments of the present invention, the surfactant is selected from a wide range for step (2), and preferably, the surfactant is an anionic surfactant and/or a cationic surfactant.
Further preferably, the anionic surfactant is at least one selected from the group consisting of carboxylate surfactants, sulfonate surfactants, sulfate surfactants, phosphate surfactants and N-acylaminocarboxylate surfactants. Examples include, but are not limited to, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium alkyl polyoxyethylene ether sulfate, sodium fatty acid.
Further preferably, the cationic surfactant is selected from at least one of an ammonium salt type surfactant, a quaternary ammonium salt type surfactant and a heterocyclic type surfactant. Examples include, but are not limited to, dodecyltrimethyl ammonium chloride (bromide), hexadecyltrimethyl ammonium bromide.
In some embodiments of the present invention, the amount of the solution containing the organic titanium source in step (3) is not particularly limited as long as a second ceramic fiber filter tube loaded with both large-particle titania and small-particle titania and having gaps between the large-particle titania filled with the small-particle titania so as to connect the large-particle titania and the small-particle titania is obtained, and preferably, the volume ratio of the solution containing the organic titanium source to the modified ceramic fiber filter tube is 1 to 20: 1, preferably 1 to 10: 1.
in some embodiments of the present invention, the organic titanium source in step (3) is selected from a wide range, and preferably, the organic titanium source is selected from at least one of titanium isopropoxide, tetrabutyl titanate ethanol and titanium polysiloxane, and more preferably, titanium isopropoxide. In this preferred case, it is more advantageous to obtain the second ceramic fiber filter tube loaded with both large-particle titanium dioxide and small-particle titanium dioxide, and the small particles are filled in the gaps between the large particles and the large particles are connected together.
The present invention is not particularly limited as long as a uniform and stable solution can be formed by mixing an organic titanium source with a solvent to form the solution containing the organic titanium source in the step (3). Preferably, the preparation process of the solution containing the organic titanium source of step (3) comprises: mixing an organic titanium source with a solvent, and then adding an acid solution to the mixture to obtain a solution containing the organic titanium source. The mixing according to the invention can be carried out under stirring. According to the invention, the hydrolysis of the organic titanium source can be effectively inhibited by adding the acid liquor, so that the solution containing the organic titanium source can be better obtained.
In some embodiments of the present invention, it is preferable that the volume ratio of the organic titanium source to the solvent and the acid solution is 1: 5-15: 0.5 to 3, more preferably 1: 6-12: 1-2.5. In this preferable case, the solution containing the organic titanium source can be obtained more favorably.
The solvent is selected from a wide range, and preferably, the solvent is selected from at least one of ethanol, methanol, propanol and isopropanol, and more preferably ethanol.
In the present invention, the acid in the acid solution is selected from a wide range, and is preferably an inorganic acid and/or an organic acid, more preferably at least one of acetic acid, oxalic acid, and hydrochloric acid, and even more preferably acetic acid.
In the invention, the solution containing the manganese source and/or the vanadium source and the M source in the step (4) means that the solution in the step (4) may contain the manganese source and the M source, may also contain the vanadium source and the M source, and may also contain the manganese source, the vanadium source and the M source.
The invention is not particularly limited to the mixing of the manganese source and/or vanadium source and M source with the solvent to form the solution containing the manganese source and/or vanadium source and M source in step (4), as long as a uniform and stable solution can be formed, for example, the manganese source and M source may be added to the solvent in sequence or simultaneously; or sequentially adding a vanadium source and an M source into the solvent or simultaneously adding the vanadium source and the M source; the manganese source, vanadium source and M source may also be added to the solvent in sequence or simultaneously. The solvent used for forming the solution of the manganese source and/or vanadium source and the M source in step (4) is not particularly limited in the present invention, and is preferably water, more preferably deionized water, in view of saving the production cost. The mixing according to the invention can be carried out under stirring.
In some embodiments of the present invention, the amount of the solution containing the manganese source and/or the vanadium source and the M source in step (4) is not particularly limited as long as manganese and/or vanadium and M (including at least one of Mo, W, Ce, Fe, Nb, Ni and Co) can be loaded on the ceramic fiber filter tube in a predetermined amount, and preferably, the volume ratio of the solution containing the manganese source and/or the vanadium source and the M source to the second ceramic fiber filter tube is 1 to 20: 1, more preferably 1 to 18: 1.
in some embodiments of the invention, preferably, TiO is used2The mass ratio of the total amount of the inorganic titanium source and the organic titanium source to the manganese source, the vanadium source and the M source in terms of oxides is 40-99: 0-30: 0-10: 0.001 to 20, more preferably 57 to 90: 10-25: 3-8: 2-10. In this preferable case, a catalyst having a further higher denitration activity can be obtained.
According to a particular embodiment of the invention, the source of manganese is selected from at least one of manganese sulphate, manganese acetate, manganese carbonate and manganese nitrate.
According to a specific embodiment of the present invention, the vanadium source is selected from at least one of sodium metavanadate, ammonium metavanadate and potassium metavanadate.
When ammonium metavanadate is used as a vanadium source, monoethanolamine needs to be further added, and then heating is carried out for dissolution, wherein the mass ratio of the monoethanolamine to the ammonium metavanadate is (0.5-2): 3. according to the invention, monoethanolamine is added for dissolving ammonium metavanadate. The heating temperature in the present invention is not particularly limited, and may be conventionally selected in the art, and is preferably 60 to 100 ℃.
According to a particular embodiment of the invention, the molybdenum source is selected from at least one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum nitrate, molybdenum chloride and molybdenum sulfate.
According to a specific embodiment of the present invention, the tungsten source is selected from at least one of ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungsten nitrate, tungsten chloride, and tungsten sulfate.
According to a specific embodiment of the present invention, the cerium source is at least one selected from the group consisting of cerous chloride, cerium nitrate, cerium ammonium nitrate and cerium sulfate.
According to a specific embodiment of the present invention, the iron source is selected from at least one of ferric nitrate, ferric chloride and ferric sulphate.
According to a specific embodiment of the present invention, the niobium source is at least one selected from the group consisting of niobium oxalate, niobium nitrate and niobium acetate.
According to a particular embodiment of the invention, the nickel source is nickel sulphate and/or nickel chloride.
According to a specific embodiment of the present invention, the cobalt source is selected from at least one of cobalt sulfate, cobalt chloride and cobalt nitrate.
In some embodiments of the present invention, preferably, the conditions of the first impregnation, the second impregnation, the third impregnation and the fourth impregnation comprise: the vacuum degree is 1-50kPa, preferably 5-30 kPa; the time is 0.5-24h, preferably 1-3 h.
Preferably, the conditions of the first drying, the second drying and the third drying include: the temperature is 60-250 ℃, preferably 80-150 ℃; the time is 1-10h, preferably 2-5 h.
Preferably, the fourth drying conditions include: the temperature is 80-120 ℃, preferably 90-100 ℃; the time is 1-12h, preferably 1-3 h.
Preferably, the conditions of the first firing, the second firing and the third firing include: the temperature is 400-650 ℃, preferably 450-550 ℃; the time is 2-10h, preferably 3-5 h. In the invention, the roasting is heated to a specified roasting temperature by adopting a temperature programming mode, preferably, the heating rate is 1-20 ℃/min, more preferably 5 ℃/min.
In the present invention, the conditions of the first impregnation, the second impregnation, the third impregnation and the fourth impregnation may be the same and may be different; the conditions of the first drying, the second drying, the third drying and the fourth drying may be the same and may be different; the conditions of the first roasting, the second roasting and the third roasting can be the same or different, and can be selected by a person skilled in the art according to actual conditions.
In some embodiments of the present invention, preferably, before the first impregnation of the ceramic fiber filter tube with the solution containing the inorganic titanium source in step (1), the method further comprises pretreating the ceramic fiber filter tube by sequentially ultrasonically cleaning and drying the ceramic fiber filter tube.
The equipment used for the ultrasonic cleaning is not particularly limited in the invention, and can be selected conventionally in the field, and preferably, the time for the ultrasonic cleaning is 30-100 min.
In the present invention, the drying conditions are not particularly limited, and preferably, the drying conditions include: the temperature is 80-200 ℃ and the time is 1-5 h.
According to a preferred embodiment of the present invention, a stepwise preparation method of a ceramic fiber filter tube catalyst comprises:
(1) placing the ceramic fiber filter tube in deionized water, performing ultrasonic cleaning for 30-100min, and drying at 80-200 deg.C for 1-5 h;
(2) soaking the ceramic fiber filter tube for 1-3h under the vacuum degree of 5-30kPa by using a solution containing an inorganic titanium source with the concentration of 5-20 wt%, wherein the volume ratio of the solution containing the inorganic titanium source to the ceramic fiber filter tube is 1-12: 1, drying at 80-150 ℃ for 2-5h, and roasting at 550 ℃ of 450-5 h to obtain a first ceramic fiber filter tube loaded with large-particle titanium dioxide with the particle size of 30-50 nm;
(3) soaking the first ceramic fiber filter tube for 1-3h by using a solution containing a surfactant with the concentration of 2-4 wt% under the vacuum degree of 5-30kPa, wherein the volume ratio of the solution containing the surfactant to the first ceramic fiber filter tube is 1-15: 1, drying for 2-5h at the temperature of 80-150 ℃ to obtain a modified ceramic fiber filter tube;
(4) mixing an organic titanium source and a solvent, and then adding an acid solution into the mixture so that the volume ratio of the organic titanium source to the solvent to the acid solution is 1: 6-12: 1-2.5, obtaining a solution containing an organic titanium source, and then soaking the modified ceramic fiber filter tube for 1-3h under the vacuum degree of 5-30kPa by using the solution containing the organic titanium source, wherein the volume ratio of the solution containing the organic titanium source to the modified ceramic fiber filter tube is 1-10: 1, drying at 80-150 ℃ for 2-5h, and roasting at 550 ℃ of 450-5 ℃ for 3-5h to obtain a second ceramic fiber filter tube;
(5) mixing a manganese source and/or a vanadium source and an M source (M is at least one of Mo, W, Ce, Fe, Nb, Ni and Co) with a solvent to obtain TiO2The mass ratio of the total amount of the inorganic titanium source and the organic titanium source to the manganese source, the vanadium source and the M source in terms of oxides is 57-90: 10-25: 3-8: 2-10, obtaining a solution containing a manganese source and/or a vanadium source and an M source, and then soaking the second ceramic fiber filter tube for 1-3 hours by adopting the solution containing the manganese source and/or the vanadium source and the M source under the vacuum degree of 5-30kPa, wherein the volume ratio of the solution containing the manganese source and/or the vanadium source and the M source to the second ceramic fiber filter tube is 1-18: 1, drying at 90-100 ℃ for 1-3h, heating to 450-550 ℃ at the heating rate of 1-20 ℃/min, and roasting for 3-5h to obtain the ceramic fiber filter tube catalyst.
The second aspect of the invention provides a ceramic fiber filter tube catalyst prepared by the method provided by the invention, wherein the content of the ceramic fiber filter tube is 74-82 wt%, the content of titanium dioxide is 12-18 wt%, and the content of active components is 6-14 wt% calculated by oxides, wherein the active components comprise Mn and/or V and at least one selected from Mo, W, Ce, Fe, Nb, Ni and Co; the specific surface area of the catalyst is 110-300m2The pore volume of the catalyst is 0.1-0.4cm3(ii) in terms of/g. According to the invention, the titanium dioxide layer of the ceramic fiber filter tube catalyst prepared by the method contains large particles with the particle size of 30-50nm and small particles with the particle size of 5-20nm, the small particles are filled in gaps among the large particles, and the large particles and the small particles are connected together, so that the ceramic tube substrate and the denitration catalyst are combined more firmly, the catalyst has larger specific surface area and pore volume, and the denitration activity of the ceramic fiber filter tube catalyst is better. In the present invention, the specific surface area and pore volume of the catalyst are measured by BET; the content of each component in the catalyst was determined by XRF.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
Measuring the content of each component in the catalyst by adopting an X-ray fluorescence spectrometer (XRF);
the specific surface area and pore volume of the catalyst were determined by BET.
Example 1
(1) Placing the ceramic fiber filter tube in deionized water for ultrasonic cleaning for 30min, and then drying at 80 ℃ for 5h for later use;
(2) soaking the ceramic fiber filter tube for 3 hours at a vacuum degree of 5kPa by adopting a solution containing titanium sulfate with the concentration of 5 wt%, wherein the volume ratio of the solution containing titanium sulfate to the ceramic fiber filter tube is 12: 1, drying at 80 ℃ for 5h, and roasting at 450 ℃ for 5h to obtain a first ceramic fiber filter tube loaded with large-particle titanium dioxide with the particle size of 30-50 nm;
(3) soaking the first ceramic fiber filter tube for 3 hours under the condition that the vacuum degree is 5kPa by adopting a solution containing sodium dodecyl benzene sulfonate with the concentration of 2 wt%, wherein the volume ratio of the solution containing sodium dodecyl benzene sulfonate to the first ceramic fiber filter tube is 15: 1, drying at 80 ℃ for 5 hours to obtain a modified ceramic fiber filter tube;
(4) mixing titanium isopropoxide with an ethanol solution, and then adding an acetic acid solution to the obtained mixture so that the volume ratio of the titanium isopropoxide to the ethanol solution and the acetic acid solution is 1: 6: 1, obtaining a solution containing titanium isopropoxide; and then soaking the modified ceramic fiber filter tube for 3 hours under the condition that the vacuum degree is 5kPa by adopting the solution containing the titanium isopropoxide, wherein the volume ratio of the solution containing the titanium isopropoxide to the modified ceramic fiber filter tube is 10: 1, drying at 80 ℃ for 5h, and roasting at 450 ℃ for 5h to obtain a second ceramic fiber filter tube simultaneously loaded with large-particle titanium dioxide with the particle size of 30-50nm and small-particle titanium dioxide with the particle size of 5-20 nm;
(5) placing ammonium metavanadate in deionized water, and adding monoethanolamine so that the mass ratio of monoethanolamine to ammonium metavanadate is 0.5: 3, dissolving the mixture by heating at 80 ℃, and then adding M salt (ammonium metatungstate)) So as to obtain TiO2The mass ratio of the total amount of titanium sulfate and titanium isopropoxide used to ammonium metavanadate and M salt (ammonium metatungstate) in terms of oxides is 90: 3: 7, fully stirring to obtain a solution containing ammonium metavanadate and ammonium metatungstate; then soaking the second ceramic fiber filter tube for 3 hours under the condition that the vacuum degree is 5kPa by adopting the solution containing ammonium metavanadate and ammonium metatungstate, wherein the volume ratio of the solution containing ammonium metavanadate and ammonium metatungstate to the second ceramic fiber filter tube is 18: 1, drying at 90 ℃ for 3h, heating to 450 ℃ at a heating rate of 5 ℃/min, and roasting for 5h to obtain the ceramic fiber filter tube catalyst.
In the obtained ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 82 wt%, the content of titanium dioxide is 12 wt%, and the content of active components (including vanadium trioxide and tungsten oxide) is 6 wt%; the specific surface area of the obtained ceramic fiber filter tube catalyst is 250m2Per g, pore volume of 0.35cm3/g。
FIG. 1 is an SEM image of a second ceramic fiber filter tube loaded with large-particle titanium dioxide having a particle size of 30-50nm and small-particle titanium dioxide having a particle size of 5-20nm, which is prepared in example 1 of the present invention, and it can be seen from FIG. 1 that the small-particle titanium dioxide is filled in gaps between the large-particle titanium dioxide and the large-particle titanium dioxide are connected together to form a titanium dioxide carrier firmly combined with the ceramic fiber filter tube, so that the ceramic tube substrate is firmly combined with the denitration catalyst, and the denitration catalyst is not easily dropped off during the filtration of flue gas and the blowback; and the active components of the catalyst are uniformly dispersed, so that the denitration activity of the ceramic tube catalyst is improved.
Example 2
(1) Placing the ceramic fiber filter tube in deionized water for ultrasonic cleaning for 100min, and then drying for 1h at 200 ℃ for standby;
(2) and (2) dipping the ceramic fiber filter tube for 1h under the vacuum degree of 30kPa by adopting a solution containing 20 wt% of titanium sulfate, wherein the volume ratio of the solution containing titanium sulfate to the ceramic fiber filter tube is 1: 1, drying at 150 ℃ for 2h, and roasting at 550 ℃ for 3h to obtain a first ceramic fiber filter tube loaded with large-particle titanium dioxide with the particle size of 30-50 nm;
(3) dipping the first ceramic fiber filter tube for 1h under the vacuum degree of 30kPa by adopting a solution containing 4 wt% of cetyl trimethyl ammonium bromide, wherein the volume ratio of the solution containing the cetyl trimethyl ammonium bromide to the first ceramic fiber filter tube is 1: 1, drying for 2 hours at 150 ℃ to obtain a modified ceramic fiber filter tube;
(4) mixing titanium isopropoxide with an ethanol solution, and then adding an acetic acid solution to the obtained mixture so that the volume ratio of the titanium isopropoxide to the ethanol solution and the acetic acid solution is 1: 12: 2.5, obtaining a solution containing titanium isopropoxide; and then soaking the modified ceramic fiber filter tube for 1h under the condition that the vacuum degree is 30kPa by adopting the solution containing titanium isopropoxide, wherein the volume ratio of the solution containing titanium isopropoxide to the modified ceramic fiber filter tube is 1: 1, drying at 150 ℃ for 2h, and roasting at 550 ℃ for 3h to obtain a second ceramic fiber filter tube loaded with large-particle titanium dioxide with the particle size of 30-50nm and small-particle titanium dioxide with the particle size of 5-20 nm;
(5) placing ammonium metavanadate in deionized water, and adding monoethanolamine so that the mass ratio of monoethanolamine to ammonium metavanadate is 2: 3, dissolving by heating at 80 deg.C, and adding M salt (ammonium metatungstate) to make into TiO2The mass ratio of the total amount of titanium sulfate and titanium isopropoxide to ammonium metavanadate and M salt (ammonium metatungstate) in terms of oxides was 82: 8: 10, fully stirring to obtain a solution containing ammonium metavanadate and ammonium metatungstate; then adopting the solution containing ammonium metavanadate and ammonium metatungstate to dip the second ceramic fiber filter tube for 1h under the condition that the vacuum degree is 30kPa, wherein the volume ratio of the solution containing ammonium metavanadate and ammonium metatungstate to the second ceramic fiber filter tube is 1: 1, drying at 100 ℃ for 1h, heating to 550 ℃ at the heating rate of 5 ℃/min, and roasting for 3h to obtain the ceramic fiber filter tube catalyst. SEM observation was performed, and similar observation results to those of FIG. 1 were obtained.
In the obtained ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 75 wt%, the content of titanium dioxide is 18 wt%, and the content of active components (including vanadium trioxide and tungsten oxide) is 7 wt%; the specific surface area of the obtained ceramic fiber filter tube catalyst is 280m2Per g, pore volume of 0.3cm3/g。
Example 3
(1) Placing the ceramic fiber filter tube in deionized water, carrying out ultrasonic cleaning for 70min, and then drying for 3h at 140 ℃ for later use;
(2) dipping the ceramic fiber filter tube for 2 hours at the vacuum degree of 18kPa by adopting a solution containing 15 wt% of titanium sulfate, wherein the volume ratio of the solution containing titanium sulfate to the ceramic fiber filter tube is 6: 1, drying at 120 ℃ for 3.5h, and roasting at 500 ℃ for 4h to obtain a first ceramic fiber filter tube loaded with large-particle titanium dioxide with the particle size of 30-50 nm;
(3) and (2) soaking the first ceramic fiber filter tube for 2 hours at the vacuum degree of 18kPa by using a solution containing sodium dodecyl sulfate with the concentration of 3 wt%, wherein the volume ratio of the solution containing sodium dodecyl sulfate to the first ceramic fiber filter tube is 10: 1, drying at 120 ℃ for 3.5 hours to obtain a modified ceramic fiber filter tube;
(4) mixing titanium isopropoxide with an ethanol solution, and then adding an acetic acid solution to the obtained mixture so that the volume ratio of the titanium isopropoxide to the ethanol solution and the acetic acid solution is 1: 9: 1.5, obtaining a solution containing titanium isopropoxide; and then soaking the modified ceramic fiber filter tube for 2 hours under the condition that the vacuum degree is 18kPa by adopting the solution containing the titanium isopropoxide, wherein the volume ratio of the solution containing the titanium isopropoxide to the modified ceramic fiber filter tube is 5: 1, drying at 120 ℃ for 3.5h, and roasting at 500 ℃ for 4h to obtain a second ceramic fiber filter tube simultaneously loaded with large-particle titanium dioxide with the particle size of 30-50nm and small-particle titanium dioxide with the particle size of 5-20 nm;
(5) manganese nitrate, M salts (cerium nitrate and ferric nitrate) were mixed with deionized water to make TiO2The mass ratio of the total amount of titanium sulfate and titanium isopropoxide to manganese nitrate, M salts (cerium nitrate and iron nitrate) in terms of oxides was 65: 25: 10, fully stirring to obtain a solution containing manganese nitrate, cerium nitrate and ferric nitrate; and then, dipping the second ceramic fiber filter tube for 2 hours under the vacuum degree of 18kPa by using the solution containing manganese nitrate, cerium nitrate and ferric nitrate, wherein the volume ratio of the solution containing manganese nitrate, cerium nitrate and ferric nitrate to the second ceramic fiber filter tube is 9: 1, drying at 90 deg.C for 3h, heating to 500 deg.C at a heating rate of 5 deg.C/min, and bakingAnd (4) burning for 4 hours to obtain the ceramic fiber filter tube catalyst. SEM observation was performed, and similar observation results to those of FIG. 1 were obtained.
In the obtained ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 76 wt%, the content of titanium dioxide is 14 wt%, and the content of active components (including manganese oxide, cerium oxide and iron oxide) is 10 wt%; the specific surface area of the obtained ceramic fiber filter tube catalyst is 230m2Per g, pore volume of 0.38cm3/g。
Example 4
The same procedure as in example 1 was followed, except that the volume ratio of the solution containing sodium dodecylbenzenesulfonate in step (3) to the first ceramic fiber filter tube was changed to 20: 1, obtaining the ceramic fiber filter tube catalyst. Wherein the obtained second ceramic fiber filter tube was subjected to SEM observation, and the observation results were similar to those of fig. 1.
In the obtained ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 81 wt%, the content of titanium dioxide is 13 wt%, and the content of active components (comprising vanadium trioxide and tungsten oxide) is 6 wt%; the specific surface area of the obtained ceramic fiber filter tube catalyst is 180m2Per g, pore volume of 0.25cm3/g。
Example 5
According to the same manner as in example 1, except for replacing the solution containing sodium dodecylbenzenesulfonate having a concentration of 2% by weight in step (3) with the solution containing sodium dodecylbenzenesulfonate having a concentration of 1% by weight, a ceramic fiber filter tube catalyst was obtained. Wherein the obtained second ceramic fiber filter tube was subjected to SEM observation, and the observation results were similar to those of fig. 1.
In the obtained ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 80 wt%, the content of titanium dioxide is 13 wt%, and the content of active components (including vanadium trioxide and tungsten oxide) is 7 wt%; the specific surface area of the obtained ceramic fiber filter tube catalyst is 200m2Per g, pore volume of 0.22cm3/g。
Example 6
The same procedure as in example 1 was followed, except that the amounts of the ethanol solution and the acetic acid solution used in step (4) were adjusted so that the volume ratio of titanium isopropoxide to the ethanol solution and the acetic acid solution was 1: 5: and 3, obtaining the ceramic fiber filter tube catalyst. Wherein the obtained second ceramic fiber filter tube was subjected to SEM observation, and the observation results were similar to those of fig. 1.
In the obtained ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 78 wt%, the content of titanium dioxide is 14 wt%, and the content of active components (including vanadium trioxide and tungsten oxide) is 8 wt%; the specific surface area of the obtained ceramic fiber filter tube catalyst is 150m2Per g, pore volume of 0.31cm3/g。
Example 7
The same procedure as in example 1 was conducted except that the amounts of ammonium metavanadate and ammonium metatungstate used in step (5) were adjusted to TiO2The mass ratio of the total usage of the titanium sulfate and the titanium isopropoxide to the ammonium metavanadate and the ammonium metatungstate calculated by oxides is 96: 2.5: 1.5, obtaining the ceramic fiber filter tube catalyst. Wherein the obtained second ceramic fiber filter tube was subjected to SEM observation, and the observation results were similar to those of fig. 1.
In the obtained ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 81 wt%, the content of titanium dioxide is 13 wt%, and the content of active components (including vanadium trioxide and tungsten oxide) is 6 wt%; the specific surface area of the obtained ceramic fiber filter tube catalyst is 130m2Per g, pore volume of 0.35cm3/g。
Comparative example 1
Following the same procedure as in example 2, except that step (3) was omitted and steps (2) and (4) were mixed, specifically:
placing the ceramic fiber filter tube in deionized water for ultrasonic cleaning for 100min, and then drying for 1h at 200 ℃ for standby;
mixing titanium isopropoxide with an ethanol solution, and then adding an acetic acid solution to the obtained mixture so that the volume ratio of the titanium isopropoxide to the ethanol solution and the acetic acid solution is 1: 12: 2.5, obtaining a solution containing titanium isopropoxide; mixing a solution of titanium isopropoxide with a solution containing 20 wt% of titanium sulfate to obtain a steeping liquor, and steeping the ceramic fiber filter tube for 1 hour under the condition that the vacuum degree is 30kPa by adopting the steeping liquor, wherein the volume ratio of the steeping liquor to the ceramic fiber filter tube is 1: 1, drying at 150 ℃ for 2h, and roasting at 550 ℃ for 3h to obtain a first ceramic fiber filter tube loaded with titanium dioxide with the particle size of 100 nm;
placing ammonium metavanadate in deionized water, and adding monoethanolamine so that the mass ratio of monoethanolamine to ammonium metavanadate is 2: 3, dissolving by heating at 80 deg.C, and adding M salt (ammonium metatungstate) to make into TiO2The mass ratio of the total amount of titanium sulfate and titanium isopropoxide to ammonium metavanadate and M salt (ammonium metatungstate) in terms of oxides was 82: 8: 10, fully stirring to obtain a solution containing ammonium metavanadate and ammonium metatungstate; then adopting the solution containing ammonium metavanadate and ammonium metatungstate to dip the first ceramic fiber filter tube for 1h under the condition that the vacuum degree is 30kPa, wherein the volume ratio of the solution containing ammonium metavanadate and ammonium metatungstate to the first ceramic fiber filter tube is 1: 1, drying at 100 ℃ for 1h, heating to 550 ℃ at the heating rate of 5 ℃/min, and roasting for 3h to obtain the ceramic fiber filter tube catalyst.
In the obtained ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 75 wt%, the content of titanium dioxide is 18 wt%, and the content of active components (including vanadium trioxide and tungsten oxide) is 7 wt%; the specific surface area of the obtained ceramic fiber filter tube catalyst is 70m2Per g, pore volume of 0.5cm3/g。
Comparative example 2
Following the same procedure as in example 2, except that steps (3) and (4) were omitted, specifically:
placing the ceramic fiber filter tube in deionized water for ultrasonic cleaning for 100min, and then drying for 1h at 200 ℃ for standby;
and (2) dipping the ceramic fiber filter tube for 1h under the vacuum degree of 30kPa by adopting a solution containing 20 wt% of titanium sulfate, wherein the volume ratio of the solution containing titanium sulfate to the ceramic fiber filter tube is 1: 1, drying at 150 ℃ for 2h, and roasting at 550 ℃ for 3h to obtain a first ceramic fiber filter tube loaded with large-particle titanium dioxide with the particle size of 30-50 nm;
placing ammonium metavanadate into deionized water, and adding monoethanolamine so that the mass ratio of monoethanolamine to ammonium metavanadate is 2: 3, dissolving by heating at 80 deg.C, and adding M salt (ammonium metatungstate) to make into TiO2The mass ratio of the total amount of titanium sulfate and titanium isopropoxide to ammonium metavanadate and M salt (ammonium metatungstate) in terms of oxides was 82: 8: 10, fully stirring to obtain a solution containing ammonium metavanadate and ammonium metatungstate; then adopting the solution containing ammonium metavanadate and ammonium metatungstate to dip the first ceramic fiber filter tube for 1h under the condition that the vacuum degree is 30kPa, wherein the volume ratio of the solution containing ammonium metavanadate and ammonium metatungstate to the first ceramic fiber filter tube is 1: 1, drying at 100 ℃ for 1h, heating to 550 ℃ at the heating rate of 5 ℃/min, and roasting for 3h to obtain the ceramic fiber filter tube catalyst.
In the obtained ceramic fiber filter tube catalyst, the content of the ceramic fiber filter tube is 75 wt%, the content of titanium dioxide is 18 wt%, and the content of active components (including vanadium trioxide and tungsten oxide) is 7 wt%; the specific surface area of the obtained ceramic fiber filter tube catalyst is 90m2Per g, pore volume of 0.68cm3/g。
Test example 1
The test example was used to evaluate the denitration activity of the ceramic fiber filter tube catalysts prepared in the above examples and comparative examples in a denitration reactor under the conditions of laboratory simulated flue gas, and the evaluation results are shown in table 1.
Simulating the test conditions of the flue gas: NO: 300Vppm, NH3：300Vppm、O2：3V％、H2O：10V％、SO2: 100Vppm, and the test temperatures are 200 ℃, 250 ℃, 300 ℃ and 350 ℃. Sampling points are respectively arranged at the inlet and the outlet of the denitration reaction device, and NO at the inlet is tested by an infrared Fourier Transform (FTIR) spectrum analyzer (MKS 2030 continuous gas analyzer)xConcentration and outlet NOxConcentration, and tested and calculated according to the following formula:
wherein η represents the NO conversion in%;
NOxinindicating an inletNOxIn Vppm;
NOxoutNO showing ExitxIn Vppm.
Test example 2
The test examples were used to evaluate the soot removal of the ceramic fiber filter tube catalysts prepared in the above examples and comparative examples, and the evaluation results are shown in table 1.
The specific test method comprises the following steps: the sample is heated to constant weight at 120 ℃ and weighed as m1(ii) a Cooling to room temperature for 1h, uniformly and slowly blowing with 0.55 +/-0.05 MPa compressed air (air gun is not more than 3cm away from the outer surface of the ceramic tube) for one week (at least 3 cycles), observing until no dust falls off from the ceramic fiber filter tube catalyst, heating the sample at 120 ℃ for 1h again, weighing, and recording as m2(ii) a The initial ceramic fiber filter tube catalyst mass was weighed and recorded as m3. The powder removal rate is calculated according to the following formula:
TABLE 1
As can be seen from the results in table 1, the ceramic fiber filter tube is repeatedly impregnated with inorganic titanium, a surfactant and organic titanium step by step, that is, small-particle silica can be filled in gaps between large-particle silica under the action of the surfactant, so that large-particle silica and small-particle silica are connected together, and thus titanium dioxide particles with different sizes are loaded on the ceramic fiber filter tube, and then active components are loaded, so that the ceramic tube substrate and the denitration catalyst can be firmly combined, and the denitration catalyst has a lower powder removal rate; meanwhile, the catalyst has higher specific surface area and pore volume, and the active components can be dispersed on the titanium dioxide more uniformly, so that the catalyst has higher denitration activity. In contrast, in comparative example 1, the ceramic fiber filter tube is repeatedly impregnated for many times in a manner of mixing inorganic titanium and organic titanium, or in comparative example 2, the ceramic fiber filter tube is repeatedly impregnated for many times only by using inorganic titanium, so that the prepared ceramic fiber filter tube catalyst is low in powder removal rate and poor in denitration activity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A stepwise preparation method of a ceramic fiber filter tube catalyst is characterized by comprising the following steps:
(1) carrying out first impregnation on the ceramic fiber filter tube by using a solution containing an inorganic titanium source, and then carrying out first drying and first roasting to obtain a first ceramic fiber filter tube loaded with large-particle titanium dioxide;
(2) carrying out second impregnation on the first ceramic fiber filter tube by using a solution containing a surfactant, and then carrying out second drying to obtain a modified ceramic fiber filter tube;
(3) carrying out third impregnation on the modified ceramic fiber filter tube by adopting a solution containing an organic titanium source, and then carrying out third drying and second roasting to obtain a second ceramic fiber filter tube loaded with large-particle titanium dioxide and small-particle titanium dioxide;
(4) carrying out fourth impregnation on the second ceramic fiber filter tube by adopting a solution containing a manganese source and/or a vanadium source and an M source, and then carrying out fourth drying and third roasting to obtain a ceramic fiber filter tube catalyst;
wherein M is at least one of Mo, W, Ce, Fe, Nb, Ni and Co.
2. The method according to claim 1, wherein the large particulate titanium dioxide has a particle size of 30-50nm and the small particulate titanium dioxide has a particle size of 5-20 nm.
3. The method according to claim 1 or 2, wherein in step (1), the volume ratio of the solution containing the inorganic titanium source to the ceramic fiber filter tube is 1-20: 1, preferably 1 to 12: 1;
preferably, in TiO2The concentration of the solution containing the inorganic titanium source is 5-20 wt%;
preferably, the inorganic titanium source of step (1) is selected from at least one of titanium sulfate, metatitanic acid and titanium tetrachloride, more preferably titanium sulfate.
4. The method according to any one of claims 1 to 3, wherein in the step (2), the volume ratio of the surfactant-containing solution to the first ceramic fiber filter tube is 1 to 20: 1, preferably 1 to 15: 1;
preferably, the concentration of the surfactant-containing solution of step (2) is 1 to 5 wt%, more preferably 2 to 4 wt%;
preferably, the surfactant of step (2) is an anionic surfactant and/or a cationic surfactant;
further preferably, the anionic surfactant is at least one selected from the group consisting of carboxylate surfactants, sulfonate surfactants, sulfate surfactants, phosphate surfactants and N-acylaminocarboxylate surfactants;
further preferably, the cationic surfactant is selected from at least one of an ammonium salt type surfactant, a quaternary ammonium salt type surfactant and a heterocyclic type surfactant.
5. The method according to any one of claims 1 to 4, wherein in the step (3), the volume ratio of the solution containing the organic titanium source to the modified ceramic fiber filter tube is 1 to 20: 1, preferably 1 to 10: 1;
preferably, the organic titanium source in the step (3) is at least one selected from titanium isopropoxide, tetrabutyl titanate ethanol and a titanium polysiloxane, and is more preferably titanium isopropoxide.
6. The method according to any one of claims 1 to 5, wherein the preparing of the solution containing the organic titanium source of step (3) comprises: mixing an organic titanium source with a solvent, and then adding an acid solution to the mixture to obtain a solution containing the organic titanium source.
7. The method of claim 6, wherein the volume ratio of the organic titanium source to the solvent and acid solution is 1: 5-15: 0.5 to 3, preferably 1: 6-12: 1-2.5;
preferably, the solvent is selected from at least one of ethanol, methanol, propanol and isopropanol;
preferably, the acid in the acid solution is selected from at least one of acetic acid, oxalic acid and hydrochloric acid.
8. The method as claimed in any one of claims 1 to 7, wherein in the step (4), the volume ratio of the solution containing the manganese source and/or the vanadium source and the M source to the second ceramic fiber filter tube is 1 to 20: 1, preferably 1 to 18: 1;
preferably, in TiO2The mass ratio of the total amount of the inorganic titanium source and the organic titanium source to the manganese source, the vanadium source and the M source in terms of oxides is 40-99: 0-30: 0-10: 0.001 to 20, more preferably 57 to 90: 10-25: 3-8: 2-10.
9. The method according to any one of claims 1 to 8, wherein in step (4), the manganese source is selected from at least one of manganese sulfate, manganese acetate, manganese carbonate and manganese nitrate;
preferably, the vanadium source is selected from at least one of sodium metavanadate, ammonium metavanadate and potassium metavanadate;
preferably, the molybdenum source is selected from at least one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, molybdenum nitrate, molybdenum chloride and molybdenum sulfate;
preferably, the tungsten source is selected from at least one of ammonium tungstate, ammonium paratungstate, tungsten nitrate, tungsten chloride, and tungsten sulfate;
preferably, the cerium source is selected from at least one of cerous chloride, cerium nitrate, ammonium cerium nitrate and cerium sulfate;
preferably, the iron source is selected from at least one of ferric nitrate, ferric chloride and ferric sulfate;
preferably, the niobium source is selected from at least one of niobium oxalate, niobium nitrate, and niobium acetate;
preferably, the nickel source is nickel sulfate and/or nickel chloride;
preferably, the cobalt source is selected from at least one of cobalt sulfate, cobalt chloride and cobalt nitrate.
10. The method of any one of claims 1-9, wherein the conditions of the first, second, third, and fourth impregnations comprise: the vacuum degree is 1-50kPa, preferably 5-30 kPa; the time is 0.5 to 24 hours, preferably 1 to 3 hours;
preferably, the conditions of the first drying, the second drying and the third drying include: the temperature is 60-250 ℃, preferably 80-150 ℃; the time is 1 to 10 hours, preferably 2 to 5 hours;
preferably, the fourth drying conditions include: the temperature is 80-120 ℃, preferably 90-100 ℃; the time is 1 to 12 hours, preferably 1 to 3 hours;
preferably, the conditions of the first firing, the second firing and the third firing include: the temperature is 400-650 ℃, preferably 450-550 ℃; the time is 2-10h, preferably 3-5 h.
11. The ceramic fiber filter tube catalyst prepared by the method of any one of claims 1 to 10, wherein the content of the ceramic fiber filter tube is 74 to 82 wt%, the content of the titanium dioxide is 12 to 18 wt%, and the content of the active component is 6 to 14 wt% calculated by oxide, based on the total amount of the ceramic fiber filter tube catalyst, wherein the active component comprises Mn and/or V and at least one selected from Mo, W, Ce, Fe, Nb, Ni and Co; the specific surface area of the catalyst is 110-300m2The pore volume of the catalyst is 0.1-0.4cm3/g。
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| CN117138559A (en) * | 2023-09-14 | 2023-12-01 | 江西兴南环保科技有限公司 | Flue gas recycling purification process based on copper-containing hazardous solid waste treatment |
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| CN116139669A (en) * | 2023-04-04 | 2023-05-23 | 北京中航天业科技有限公司 | Ceramic catalytic filter element, preparation method and flue gas multi-pollutant collaborative purification system and method based on ceramic catalytic filter element |
| CN117138559A (en) * | 2023-09-14 | 2023-12-01 | 江西兴南环保科技有限公司 | Flue gas recycling purification process based on copper-containing hazardous solid waste treatment |
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