CN105413737A - Ion exchange/impregnation continuous preparation Fe-based molecular sieve SCR catalyst - Google Patents
Ion exchange/impregnation continuous preparation Fe-based molecular sieve SCR catalyst Download PDFInfo
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- CN105413737A CN105413737A CN201510749157.9A CN201510749157A CN105413737A CN 105413737 A CN105413737 A CN 105413737A CN 201510749157 A CN201510749157 A CN 201510749157A CN 105413737 A CN105413737 A CN 105413737A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000005342 ion exchange Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005470 impregnation Methods 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 50
- 238000007598 dipping method Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- 238000010924 continuous production Methods 0.000 claims description 10
- -1 salt compound Chemical class 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 3
- UHAQRCJYQAKQEE-UHFFFAOYSA-M [O-2].[OH-].O.[Al+3].P Chemical compound [O-2].[OH-].O.[Al+3].P UHAQRCJYQAKQEE-UHFFFAOYSA-M 0.000 claims description 3
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052804 chromium Inorganic materials 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
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 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 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- GKLAGQWSCNXXKN-UHFFFAOYSA-N iron;nitrous acid Chemical compound [Fe].ON=O GKLAGQWSCNXXKN-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 150000002506 iron compounds Chemical class 0.000 abstract description 2
- 239000003426 co-catalyst Substances 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000009775 high-speed stirring Methods 0.000 abstract 1
- 150000002500 ions Chemical group 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 230000003068 static effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229960004643 cupric oxide Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process 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
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 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 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to an ion exchange/impregnation continuous preparation Fe-based molecular sieve SCR catalyst. The ion exchange/impregnation continuous preparation Fe-based molecular sieve SCR catalyst is characterized in that a specific preparation method of the catalyst comprises the following specific steps: dissolving a compound containing ferric salt in dissolved water and preparing into a metal salt solution with a certain concentration; adding a dispersing agent; adding a molecular sieve material in the solution, adding a co-catalyst metal compound material to form a solution, and increasing the solid content of an ion exchange solution to form an excessive impregnation state; heating and concentrating under the state of high-speed stirring, dehydrating and drying an aged catalyst raw material, grinding into a certain grain size, and calcining at high temperature to obtain the Fe-based molecular sieve SCR catalyst without NOx. The ion exchange-impregnation combined method is adopted, and an active component guiding-in agent and a dispersing agent are added so that the metal active components Fe are uniformly distributed in molecular sieve holes and surfaces of the molecular sieve holes; and moreover, during calcination of an iron compound, Fe has abundant valence states, and NOx conversion efficiency is high.
Description
Technical field
The present invention relates to a kind of ion-exchange/dipping continuous production Fe based molecular sieve SCR catalyst, particularly a kind of diesel motor exhaust nitrogen oxide (NO
x) SCR (SCR) catalytic purification iron-based zeolite molecular sieve catalyst material and preparation method thereof.
Background technology
The application of SCR technology on motor vehicle, is widely used in areas such as Europe, the U.S., Japan.NH
3-SCR system in the course of the work, ammonia and NO
xa series of chemical reaction can be there is, by NO
xbe reduced into nitrogen (N
2) and water.
The features such as zeolite molecular sieve has environmental friendliness, high-specific surface area, heat resistanceheat resistant function admirable, progressively become the mainstay material of SCR catalyst.By different metal-modified, meet the demand of motor vehicle NOx purified treatment.
Many research shows, iron-based zeolite molecular sieve catalyst, and copper based molecular sieve catalyst and copper iron composite molecular sieve catalyst have higher catalytic purification active to the nitrogen oxide in vehicle exhaust, have broad application prospects.
The common preparation method of metal modified molecular screen catalyst has ion-exchange and infusion process.Ion-exchange, metal ion contacts more abundant with molecular sieve, metal ion can replace the element in framework of molecular sieve effectively, thus changes the acidity of molecular sieve, and the application for catalyst provides more wide application space.But solution concentration is lower, the ion-exchange time is longer, needs repeatedly to exchange for several times if need to realize higher exchange capacity.Be unfavorable for industrialized batch production.
Infusion process content of metal is higher, and operating procedure is easy, fast, is applicable to the batch production of catalyst.Meanwhile, because metal ion solution concentration is high, catalyst material poor fluidity during incipient impregnation, bad dispersibility, easily causes local concentration too high, forms crystallization.Load to metal in duct too much time, the pore passage structure of molecular sieve may be closed, and at molecular formula surface enrichment.Reduce specific surface area of catalyst.
Coupled ion exchanges the advantage with infusion process, first carry out ion-exchange, in the skeleton entering into molecular sieve enabling the metal of modification higher or effectively pore passage structure, make metal ion evenly be dispersed in molecular sieve surface, then by improving the load capacity of catalyst active ingredient, catalyst is met operationally to the demand of catalyst.
Two kinds of methods combining are simplified the process of preparation, improve the vegetation efficiency of catalyst, high load capacity improves activity of conversion and the endurance life of catalyst.
A kind of preparation method of micron-level molecular sieve loaded nano-iron material is disclosed, by liquid phase reduction in-situ preparation Nanoscale Iron ion on molecular sieve carrier in CN103263901A patent.
CN102774850A patent discloses a kind of fast preparation method of iron content mesoporous-microporous composite molecular sieve, adopts molecular sieve and iron nitrate solution and synthesizes liquid, hydro-thermal purification synthesis.
CN102824925A patent disclosure a kind of iron-molecular sieve catalyst and application thereof, adopt organoiron compound solution, with on the method load molecular sieve carrier flooded.
CN103007998A patent discloses a kind of method prepared for nitrous oxide catalytic decomposition and reduction molecular sieve catalyst, adopts Ultrasonic Heating to realize the exchange of quick iron ion.
There are the following problems in the preparation of above-mentioned catalyst: (1) repeatedly dipping process is loaded down with trivial details, and effective active component skewness; (2) ion-exchange will be stirred through long, then through cyclic washing, filtration, oven dry, calcining, the operating time is grown and is not easy to realize a large amount of industrial volume production; (3) durability of catalyst poor-performing.
Summary of the invention
The object of this invention is to provide a kind of ion-exchange/dipping continuous production Fe based molecular sieve SCR catalyst, its method adopting ion-exchange-dipping to combine, wherein add active component imported agent and dispersant makes metal active constituent Fe in molecular sieve pores and surface distributed more even, and when iron compound is calcined, the valence state of Fe is abundanter, and NOx conversion efficiency is high; Can also as active component while the promoter metal compounds of adding improves Sulfur tolerance, NO is to the conversion of NOx in strengthening, considerably improves the activity of SCR catalyst, has higher actual application value.
Technical scheme of the present invention is achieved in that ion-exchange/dipping continuous production Fe based molecular sieve SCR catalyst, it is characterized in that concrete steps are as follows:
A) be dissolved in deionized water by iron content salt compound and be made into certain density metal salt solution, the ratio of molysite compound and deionized water is 1:1 ~ 1:6, and ammoniacal liquor regulates solution ph to OK range, between 6.5 ~ 10; Add dispersant;
B) in the solution of step a), add molecular screen material, molecular sieve urge material and a) solution proportion be 1:1 ~ 3:1, iron salt solutions is excessive, and high-speed stirred 1 ~ 5h, adds molecular screen material while stirring, stirs, and ion-exchange is carried out in overall heating; Ion-exchange time is 1 ~ 12h, the preferred time, 1 ~ 6h, and the optimum time is 2 ~ 3h, and the temperature of heating is 50 ~ 90 DEG C, and preferred temperature is 60 ~ 85 DEG C, and optimum temperature is 65 ~ 75 DEG C;
C) promoter metal compounds material is added to step b), di-iron trioxide, rare earth element are nitrate or the oxide of La, Ce, Zr, additional proportion is 1% ~ 15%, form solution, improve the solid content of ion exchange liquid, adjust ph, to OK range, between 6.5 ~ 10, forms excessive impregnation state; The time of dipping is 1 ~ 24h, and preferred dip time is 1 ~ 12h, and the more excellent time is 2 ~ 6h, and the optimum time is 2 ~ 3h;
D) under high-speed stirred state, heating is concentrated, makes mixture form incipient impregnation or micro-excessive dipping, standing, ageing; The time of dipping is 1 ~ 24h, and preferred dip time is 1 ~ 12h, and the more excellent time is 2 ~ 6h, and the optimum time is 2 ~ 3h.Standing, ageing 3 ~ 5h;
E) the catalyst raw material after ageing is carried out dewatered drying, be ground to certain particle diameter, through high-temperature calcination, namely obtain the Fe based molecular sieve SCR catalyst removing NOx; Bake out temperature is 105 ~ 150 DEG C, the temperature of high-temperature calcination is 350 ~ 550 DEG C, calcining requires to carry out in oxygen-containing atmosphere or air, and oxygen content is greater than 10%.
Described ferrous metal salt compound comprises the sulfate of iron, ferric sulfate, ferrous sulfate; The nitrate compound of iron, ferric nitrate, ferrous nitrate, nitrous acid iron, and the oxide of iron; Rare earth element is nitrate or the oxide of La, Ce, Zr; Transition metal is manganese, cobalt, the nitrate of Ti, V, W, Cu, Cr, Ni element or oxide.
Described molecular screen material skeleton structure topology code is that International Zeolite Association meeting (IZA) proposes, and comprising: MFI, MEL, CHA, BEA, FAU, LTA, MOR or their mixture; Pore size is the mesopore molecular sieve of 2 ~ 50nm, comprises and consists of silicon-aluminum oxide, silica, aluminium oxide, phosphorus aluminum oxide.
The silica alumina ratio of described molecular screen material is 20 ~ 200, and more excellent silica alumina ratio is 30 ~ 200, and optimum silica alumina ratio is 30 ~ 100.
Described ammoniacal liquor, mass fraction is 5% ~ 28%; Dispersant is low-molecular-weight alcohols, monohydric alcohol, dihydroxylic alcohols, and as ethanol, particularly, its surface tension is not more than 45dyn/cm.
Good effect of the present invention is catalyst material prepared by employing method, quantity-produced process can improve the preparation efficiency of catalyst, be conducive to industrialized batch production, ion-exchange and dipping continuous production are conducive to improving modified metal ion load effect over a molecular sieve, greatly improve the transformation efficiency of catalyst.
Through the mensuration of specific area, although through metal-modified process, the specific area of the element modified molecular sieve of carried metal, still can reach close to 200m
2/ more than g.
Catalyst has close relationship to the detergent power of nitrogen oxide and temperature, air-flow.General catalyst temperature influence is comparatively large, and low temperature can reduce the treatment effeciency of catalyst.Time air speed is high, reducing agent ammonia and catalyst contact time short, shorten with the reaction of nitrogen oxides time simultaneously, the treatment effeciency of catalyst can be reduced.The present invention selects suitable micropore and meso-hole structure molecular sieve, improves molecular sieve to the selective adsorption capacity of gas.Make catalyst at high-speed, under low exhaust temperature condition, still have very high NOx selective catalysis transformation efficiency.
Accompanying drawing explanation
Iron-based high activity molecular sieve SCR catalyst isothermal adsorption/desorption curve described in Fig. 1 embodiment 1 prepared by micro porous molecular sieve.
Iron-based high activity molecular sieve SCR catalyst isothermal adsorption/desorption curve described in Fig. 2 embodiment 4 prepared by mesopore molecular sieve.
Fig. 3 temperature is on the impact of catalyst efficiency synthesized by embodiment 1.
Fig. 4 air speed is on the impact of catalyst efficiency synthesized by embodiment 1.
Fig. 5 is embodiments of the invention 1 product S EM.
Detailed description of the invention
The present invention will be further described with embodiment with reference to the accompanying drawings below:
The molecular screen material of carried metal modification is mainly the molecular sieve of commercially available industrial mass manufacture, described molecular screen material skeleton structure topology code is that International Zeolite Association meeting (IZA) proposes, and comprising: MFI, MEL, CHA, BEA, FAU, LTA, MOR or their mixture; Pore size is the mesopore molecular sieve of 2 ~ 50nm, comprises and consists of silicon-aluminum oxide, silica, aluminium oxide, phosphorus aluminum oxide.Micropore and meso-porous molecular sieve material have higher specific area and good characterization of adsorption, Fig. 1 is the isothermal adsorption/desorption curve of the micro porous molecular sieve material of Fe based molecular sieve catalyst, the isothermal adsorption/desorption curve of the mesoporous porous molecular sieve material of Fig. 2 Fe based molecular sieve catalyst.The specific area of molecular sieve is comparatively large, and by reducing the specific area of material after metallic element modification, the BET specific surface area of the Fe based molecular sieve catalyst that the present invention is modified still has 200m
2/ more than g.Test data is in Table.This catalytic treatment that will be conducive to NOx under high-speed condition.
Catalyst has close relationship to the detergent power of nitrogen oxide and temperature, air-flow.General catalyst temperature influence is comparatively large, and low temperature can reduce the treatment effeciency of catalyst.Time air speed is high, reducing agent ammonia and catalyst contact time short, shorten with the reaction of nitrogen oxides time simultaneously, the treatment effeciency of catalyst can be reduced.The present invention selects suitable micropore and meso-hole structure molecular sieve, improves molecular sieve to the selective adsorption capacity of gas.Make catalyst at high-speed, under low exhaust temperature condition, still have very high NOx selective catalysis transformation efficiency.Temperature is shown in Fig. 3 to catalysts influence test result.The affect test result of air speed on catalyst is shown in Fig. 4, and Fig. 5 is SEM product.
Embodiment 1
Take the Fe (NO of 1000g
3)
3﹒ 9H
2o, in 2000g deionized water, adds 3500gZSM-5 molecular sieve after stirring and dissolving, stir 5h; Continuing to add 1200ml mass fraction is 10% ammoniacal liquor, after making it stir, adds 150g ethanol and continues to stir half until evenly, static dipping 2h.Then, put into disk in the oven dry of 105 DEG C, baking oven, smash in the blocks of solid of having dried and pulverizer, at being placed in Muffle furnace 550 DEG C, calcine 4h, powder grinder after calcining is further processed as the powder of particle diameter 0.5 ~ 1 micron, namely obtains iron-based high activity molecular sieve SCR catalyst.
Use fixed-bed micro-reactor, five gas analyzers carry out NH to catalyst fines
3-SCR conversion efficiency is tested, and experiment condition is: air speed 100000h
-1, NO500ppm, O
25%, NH
3500ppm.Result as shown in Figure 4.Improve air speed to 160000h
-1, result as shown in Figure 3.
Embodiment 2
Take the Fe (NO3) of 1400g
3﹒ 9H
2o, in 2500g deionized water, adds the SAPO-34 molecular sieve of 3.5kg after stirring and dissolving, stir 8h; The mass fraction continuing to add 1200ml is 15% ammoniacal liquor, after making it stir, adds 350g ethanol and continues to stir half until evenly, static dipping 24h.Continue to stir the ferric oxide powder adding the 500nm of 100g, after stirring, put into disk in the oven dry of 150 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, 6h is calcined at being placed in Muffle furnace 520 DEG C, powder grinder after calcining is further processed as the powder of particle diameter 2 ~ 5 μm, namely obtains Fe based molecular sieve catalyst.
Embodiment 3
Take the FeCl of 800g
3﹒ 6H2O is dissolved in 3000g deionized water, adds the beta-molecular sieve of 3000g after stirring and dissolving, stirs 3h; The mass fraction continuing to add 900g is 20% ammoniacal liquor, and after making it stir, 90% ethylene glycol adding 180g continues to stir half until evenly, static dipping 4h.Continue to stir the di-iron trioxide adding 1 μm of 500g, 600g cerium oxide powder, after dispersed with stirring is even, put into disk in the oven dry of 135 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 5h at being placed in Muffle furnace 500 DEG C, powder grinder after calcining is further processed as the powder that particle diameter is 2 microns, namely obtains Fe based molecular sieve catalyst.
Embodiment 4
Take the Fe (NO of 900g as shown in Figure 2
3)
3﹒ 9H
2o is dissolved in 3000g deionized water, add the MCM-41 molecular sieve of 3000g after stirring and dissolving, stir 2h; The mass fraction continuing to add 1250ml is 28% ammoniacal liquor, and after making it stir, 90% ethylene glycol adding 200g continues to stir half until evenly, static dipping 4h.Continue to stir the croci and 150g cerium oxide, the lanthanum oxide powder that add 1 micron of 150g, after stirring, put into disk in the oven dry of 140 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, 5h is calcined at being placed in Muffle furnace 450 DEG C, powder grinder after calcining is further processed as powder, namely obtains Fe based molecular sieve catalyst.
Embodiment 5
Take the Fe (NO of 1200g
3)
3﹒ 9H2O, in 3000g deionized water, adds the SSZ-13 molecular sieve of 3000g after stirring and dissolving, stir 4h; The mass fraction continuing to add 1000g is 28% ammoniacal liquor, and after making it stir, the ethanol adding 150g continues to stir half until evenly, static dipping 8h.Continue to stir the nickel nitrate adding the copper nitrate of 100g, the manganese nitrate of 150g, 50g cobalt nitrate and 150g, after stirring, put into disk in the oven dry of 140 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, 5h is calcined at being placed in Muffle furnace 450 DEG C, by the powder that powder grinder after calcining is further processed as, namely obtain Fe based molecular sieve catalyst.
Embodiment 6
Take the Fe (NO of 1200g
3)
3﹒ 9H2O, in 3000g deionized water, adds the ZSM-5 molecular sieve of 3000g after stirring and dissolving, stir 4h; The mass fraction continuing to add 1000ml is 28% ammoniacal liquor, and after making it stir, the ethanol adding 150g continues to stir half until evenly, static dipping 8h.Continue the nickel oxide stirring the cupric oxide, the manganese oxide of 50g, the chromium oxide of 50g and the 50g that add 50g, after stirring, put into disk in the oven dry of 120 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, 5h is calcined at being placed in Muffle furnace 550 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains Fe based molecular sieve catalyst.
Embodiment 7
Take the Fe (NO of 1200g
3)
3﹒ 9H2O, in 3000g deionized water, adds the ZSM-5 molecular sieve of 3000g after stirring and dissolving, stir 4h; The mass fraction continuing to add 1000ml is 28% ammoniacal liquor, and after making it stir, the ethanol adding 150g continues to stir half until evenly, static dipping 8h.Continue to stir the cupric oxide, the tungsten oxide of 50g, the titanium oxide of 50g that add 100g, after stirring, put into disk in the oven dry of 120 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, 5h is calcined at being placed in Muffle furnace 550 DEG C, powder grinder after calcining is further processed as the powder of particle diameter 1 ~ 2 micron, namely obtains Fe based molecular sieve catalyst.
Embodiment 8
Take the Fe (NO of 1200g
3)
3﹒ 9H2O, in 3kg deionized water, adds the ZSM-5 molecular sieve of 3kg after stirring and dissolving, stir 4h; The mass fraction continuing to add 1L is 28% ammoniacal liquor, and after making it stir, the ethanol adding 150g continues to stir half until evenly, static dipping 8h.Continue to stir the cupric oxide, the tungsten oxide of 100g, the vanadic anhydride of 150g that add 150g, after stirring, put into disk in the oven dry of 120 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, 3h is calcined at being placed in Muffle furnace 450 DEG C, powder grinder after calcining is further processed as the powder of particle diameter 1 ~ 2 micron, namely obtains Fe based molecular sieve catalyst.
Claims (5)
1. ion-exchange/dipping continuous production Fe based molecular sieve SCR catalyst, it is characterized in that its concrete preparation method, concrete steps are as follows:
A) be dissolved in deionized water by iron content salt compound and be made into certain density metal salt solution, the ratio of molysite compound and deionized water is 1:1 ~ 1:6, and ammoniacal liquor regulates solution ph to OK range, between 6.5 ~ 10; Add dispersant;
B) in the solution of step a), add molecular screen material, molecular sieve urge material and a) solution proportion be 1:1 ~ 3:1, iron salt solutions is excessive, and high-speed stirred 1 ~ 5h, adds molecular screen material while stirring, stirs, and ion-exchange is carried out in overall heating; Ion-exchange time is 1 ~ 12h, the preferred time, 1 ~ 6h, and the optimum time is 2 ~ 3h, and the temperature of heating is 50 ~ 90 DEG C, and preferred temperature is 60 ~ 85 DEG C, and optimum temperature is 65 ~ 75 DEG C;
C) promoter metal compounds material is added to step b), di-iron trioxide, rare earth element are nitrate or the oxide of La, Ce, Zr, additional proportion is 1% ~ 15%, form solution, improve the solid content of ion exchange liquid, adjust ph, to OK range, between 6.5 ~ 10, forms excessive impregnation state; The time of dipping is 1 ~ 24h, and preferred dip time is 1 ~ 12h, and the more excellent time is 2 ~ 6h, and the optimum time is 2 ~ 3h;
D) under high-speed stirred state, heating is concentrated, makes mixture form incipient impregnation or micro-excessive dipping, standing, ageing; The time of dipping is 1 ~ 24h, and preferred dip time is 1 ~ 12h, and the more excellent time is 2 ~ 6h, and the optimum time is 2 ~ 3h, standing, ageing 3 ~ 5h;
E) the catalyst raw material after ageing is carried out dewatered drying, be ground to certain particle diameter, through high-temperature calcination, namely obtain the Fe based molecular sieve SCR catalyst removing NOx; Bake out temperature is 105 ~ 150 DEG C, the temperature of high-temperature calcination is 350 ~ 550 DEG C, calcining requires to carry out in oxygen-containing atmosphere or air, and oxygen content is greater than 10%.
2., according to the ion-exchange described in claim 1/dipping continuous production Fe based molecular sieve SCR catalyst, it is characterized in that described ferrous metal salt compound comprises the sulfate of iron, ferric sulfate, ferrous sulfate; The nitrate compound of iron, ferric nitrate, ferrous nitrate, nitrous acid iron, and the oxide of iron; Rare earth element is nitrate or the oxide of La, Ce, Zr; Transition metal is manganese, cobalt, the nitrate of Ti, V, W, Cu, Cr, Ni element or oxide.
3. according to the ion-exchange described in claim 1/dipping continuous production Fe based molecular sieve SCR catalyst, it is characterized in that described molecular screen material skeleton structure topology code is that International Zeolite Association meeting (IZA) proposes, comprising: MFI, MEL, CHA, BEA, FAU, LTA, MOR or their mixture; Pore size is the mesopore molecular sieve of 2 ~ 50nm, comprises and consists of silicon-aluminum oxide, silica, aluminium oxide, phosphorus aluminum oxide.
4. according to the ion-exchange described in claim 1/dipping continuous production Fe based molecular sieve SCR catalyst, it is characterized in that the silica alumina ratio of described molecular screen material is 20 ~ 200, more excellent silica alumina ratio is 30 ~ 200, and optimum silica alumina ratio is 30 ~ 100.
5., according to the ion-exchange described in claim 1/dipping continuous production Fe based molecular sieve SCR catalyst, it is characterized in that described ammoniacal liquor, mass fraction is 5% ~ 28%; Dispersant is low-molecular-weight alcohols, monohydric alcohol, dihydroxylic alcohols, and as ethanol, particularly, its surface tension is not more than 45dyn/cm.
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