CN105413738A - 高能球磨法scr分子筛催化剂及其制备方法 - Google Patents
高能球磨法scr分子筛催化剂及其制备方法 Download PDFInfo
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- CN105413738A CN105413738A CN201510749161.5A CN201510749161A CN105413738A CN 105413738 A CN105413738 A CN 105413738A CN 201510749161 A CN201510749161 A CN 201510749161A CN 105413738 A CN105413738 A CN 105413738A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 70
- 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 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000003801 milling Methods 0.000 title 1
- 238000000498 ball milling Methods 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 36
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 229960004643 cupric oxide Drugs 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 206010013786 Dry skin Diseases 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
- 235000021050 feed intake Nutrition 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 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
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- -1 salt compound Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000007704 transition Effects 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
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 8
- 238000000713 high-energy ball milling Methods 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000003426 co-catalyst Substances 0.000 abstract 3
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000001913 cellulose Substances 0.000 description 9
- 229920002678 cellulose Polymers 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 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 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
- 239000012528 membrane Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- UHAQRCJYQAKQEE-UHFFFAOYSA-M [O-2].[OH-].O.[Al+3].P Chemical compound [O-2].[OH-].O.[Al+3].P UHAQRCJYQAKQEE-UHFFFAOYSA-M 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 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 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution 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
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 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
- B01J29/7615—Zeolite Beta
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种复合氧化物铁基分子筛SCR催化剂及其制备方法,其特征在于其制备方法,其特征在于,使用高能球磨法,将铜氧化物、铁氧化物,以及助催化剂金属氧化物材料与分子筛混合均匀,加入活性组分导入剂、表面分散剂进行浸渍,经球磨,经烘干、研磨、煅烧,即得到复合氧化物分子筛SCR催化剂,应用于对机动车尾气中NOx的催化净化。其简化了催化剂制备流程,采用高能球磨方法,其中添加活性组分导入剂以及分散剂使得金属活性组分在分子筛孔内及表面分布的更为均匀,且在煅烧时,金属氧化物的价态比较丰富,NOx转化效率高;添加的助催化剂金属化合物提高了耐硫性的同时还可以作为活性组分,强化NO向NO2的转化,显著地提高了SCR催化剂的活性,具有更高的实际应用价值。
Description
技术领域
本发明涉及一种高能球磨法SCR分子筛催化剂及其制备方法,特别涉及一种柴油发动机尾气氮氧化物(NOx)选择性催化还原(SCR)催化净化用复合氧化物铁基沸石分子筛催化剂材料及其制备方法。
背景技术
许多的研究表明,金属元素改性沸石分子筛催化剂,铁基、铜基分子筛催化剂以及铜铁复合分子筛催化剂对汽车尾气中的氮氧化物有较高的催化净化活性,具有广阔的应用前景。
沸石分子筛具有环境友好,高比表面积,抗热性能优良等特点,正在逐步成为SCR催化剂的主流材料。通过不同的金属改性,满足机动车NOx净化处理的需求。改性后的金属材料主要以氧化物的形式存在与分子筛催化剂的孔道或是表面。
分子筛催化剂常用的制备方法有离子交换法和浸渍法,使用金属盐,形成溶液,常用的金属盐为硝酸盐,或是氯化物等,在制备过程中,由于需要的有效成分为氧化物,硝酸根会分解产生氮氧化物,氯化物会产生氯化氢气雾,或是氯气。为了解决制备过程产生的有害废气,实现清洁,绿色制造的理念,采用高能球磨法制备催化剂是一种新兴的环保技术。
高能球磨,又称为机械力化学,一经出现,就成为制备超细材料的一种重要途径。传统上,新物质的生成、晶型转化或晶格变形都是通过高温(热能)或化学变化来实现的。机械能直接参与或引发了化学反应是一种新思路。机械化学法的基本原理是利用机械能来诱发化学反应或诱导材料组织、结构和性能的变化,以此来制备新材料。作为一种新技术,它具有明显降低反应活化能、细化晶粒、极大提高粉末活性和改善颗粒分布均匀性及增强体与基体之间界面的结合,促进固态离子扩散,诱发低温化学反应,从而提高了材料的密实度、电、热学等性能,是一种节能、高效的材料制备技术。它的研究必将推动新材料研究及相关学科的发展。就材料科学而言,机械力化学是一个有较宽广研究空间的领域。同时,目前取得的成就已足以表明该技术具有广阔的工业应用前景。
通过高能球磨,应力、应变、缺陷和大量纳米晶界、相界产生,使***储能很高(达十几kJPmol),粉末活性大大提高,甚至诱发多相化学反应。目前已在很多***中实现了低温化学反应,成功合成出新物质。
至今已经用机械化学研制出超饱和固溶体、金属间化合物、非晶态合金等各种功能材料和结构材料,也已经应用在许多高活性催化剂粉体、纳米硅酸盐复合材料等的研究中。
CN101121526A专利中公开了一种纳米Fe-ZSM-5沸石分子筛的制备方法,该方法为水热合成方式,70~120℃恒温20~60h,然后升温140~220℃再恒温10~80小时,反应时间长,温度高,难于批量化生产。
CN102125868A专利公开了一种微孔-介孔复合Fe-ZSM-5沸石分子筛催化剂的制备方法,采用水热合成方法,反应釜中在140~180℃下晶化1~5天,得到固体样品。
CN103386322A专利公开了一种用于NOx选择性催化还原的Fe-ZSM-5催化剂及其制备,也是采用有机模板剂水热合成方式制备的催化剂。
CN103599811A专利公开了一种纳米Fe-MCM-41分子筛催化剂的制备方法,使用高速分散机,分散硅***胶,水热合成制备。
CN103272628A专利公布了一种负载金属氧化物的醇解催化剂及其制法,使用的工艺方法为浸渍后煅烧工艺。
CN103086395A专利公布了一种以金属氧化为载体的SAPO系列分子筛膜制备方法,以金属氧化物为载体,通过合成液在金属氧化物表面原位水热合成分子筛膜。
上述制备Fe基分子筛催化剂虽在不同程度上提高了催化剂的性能,但也存在如下问题:(1)水热法反应时间长;(2)反应釜温度压力高,对反应条件控制要求严格;(3)制备过程中有机模板剂煅烧过程中产生有害废气。
发明内容
本发明的目的是提供一种高能球磨法SCR分子筛催化剂及其制备方法,其简化了催化剂制备流程,采用高能球磨方法,其中添加活性组分导入剂以及分散剂使得金属活性组分在分子筛孔内及表面分布的更为均匀,且在煅烧时,金属氧化物的价态比较丰富,NOx转化效率高;添加的助催化剂金属化合物提高了耐硫性的同时还可以作为活性组分,强化NO向NO2的转化,显著地提高了SCR催化剂的活性,具有更高的实际应用价值。
本发明的技术方案是这样实现的:复合氧化物铁基分子筛SCR催化剂及其制备方法,其特征在于其制备方法,具体步骤如下:
(1)将铜、铁金属氧化物的一种或是两种加入球磨罐内,选择两种氧化时,氧化铜与氧化铁的比例为1:1~4:1,按料球比1:2投料,球直径为2mm~8mm,等份等比例添加直径不同的磨球,加入无水乙醇调和固体组分形成流动浆料,无水乙醇不需要比例,球磨得到A组分,球磨2~4h;
(2)将分子筛原料加水和分散剂材料乙醇球磨,分子筛:水:分散剂比例为2:1:1~4:2:1,按料球比1:2投料,球直径为2mm~8mm,等份等比例添加直径不同的磨球;
(3)在分子筛球磨罐内加入助催化剂金属盐化合物,稀土元素为La,Ce,Zr氧化物1%~10%;过渡金属为锰、钴、Ti、V、W、Cu、Cr、Ni元素的氧化物,可以是一种或是多种的混合,单一过渡元素添加量为1%~10%,两种以上时总添加量不大于10%,Mn:Co:Ti:V:W:Cu:Cr:Ni比例为1:1:1:1:1:1:1:1~2:1:1:0.5:1.5:2:1:2,由于测试数量限制,添加的材料也可以是此比例以外的组合配比,测试材料的pH值,使用氨水调节pH值至需要范围6~8,球磨1~2h;
(4)将A组分加入步骤(3)中,继续球磨2~6h,然后加入步骤(2)分子筛原料,继续球磨6~16h,然后得到含有催化剂元素的分子筛材料;
(5)含有催化剂元素的分子筛材料,经105℃脱水烘干、550℃煅烧、研磨后得到粒径为1~2微米的,去除氮氧化物的金属氧化物改性的分子筛SCR催化剂。
本发明的积极效果是其简化了催化剂制备流程,采用高能球磨方法,其中添加活性组分导入剂以及分散剂使得金属活性组分在分子筛孔内及表面分布的更为均匀,且在煅烧时,金属氧化物的价态比较丰富,NOx转化效率高;添加的助催化剂金属化合物提高了耐硫性的同时还可以作为活性组分,强化NO向NO2的转化,显著地提高了SCR催化剂的活性,具有更高的实际应用价值。
附图说明
图1结构微孔分子筛等温吸附/脱附曲线。
图2介孔分子筛材料等温吸附/脱附曲线。
图3温度对催化剂效率的影响。
图4为本发明的实施例1产物SEM。
具体实施方式
下面结合附图与实施例对本发明做进一步说明:在下述的具体事例描述中,给出了大量具体的细节以便于更为深刻的理解本发明。然而,对于本领域技术人员来说显而易见的是,本发明可以无需一个或多个这些细节而得以实施。
负载金属改性的分子筛材料主要为市售的工业批量生产的分子筛材料,所述分子筛材料骨架拓扑学结构代码为国际沸石联合会(IZA)提出,包括:MFI、MEL、CHA、BEA、FAU、LTA、MOR或是它们的混合物;孔道尺寸为2~100nm的介孔分子筛,包括组成为硅-铝氧化物、氧化硅、氧化铝、磷铝氧化物。
具体的分子筛型号有ZSM-5,ZSM-11,13X-4A,13X-5A,SAPO-13,SAPO-18,SAPO-33,SAPO-34,SSZ-11,SSZ-13等具有微孔和介孔的分子筛。
微孔和介孔分子筛材料具有较高的比表面积和良好的吸附特性,图1是分子筛催化剂的微孔和介孔分子筛材料的等温吸附/脱附曲线。可以看出分子筛材料符合Ⅰ型等温吸附曲线Ⅰ。微孔的形成表明存在金属材料进入分子筛材料的孔道结构内部的可能。图1显示,催化剂材料在较低相对压力时就具有很高的吸附量,催化剂的吸附活性较高。
图2符合Ⅳ型等温吸附曲线,存在滞后环,表明存在金属氧化组分由于氧化物的存在,形成新型的孔结构和孔尺寸,表明氧化物材料微观也是存在多孔性。根据曲线孔尺寸主要为中孔至大孔结构。
表1比表面积测试数据
样品名 | BET比表面积(m2/g) |
实施例1 | 229 |
实施例2 | 229 |
实施例3 | 247 |
实施例4 | 218 |
实施例5 | 257 |
实施例6 | 219 |
通过对比表面积的测定,显示由于负载金属元素改性分子筛的比表面积有所下降,但是催化剂的比表面积仍然能够达到200m2/g以上。测试数据见表1。
催化剂对氮氧化物的净化能力与温度、气流有密切的关系。一般的催化剂受温度影响较大,低温会降低催化剂的处理效率。空速高的时候,还原剂氨气与催化剂接触时间短,与氮氧化物反应时间同时缩短,会降低催化剂的处理效率。本发明选择合适的微孔和介孔结构分子筛,提高分子筛对气体的选择性吸附能力。使催化剂在高空速,低排气温度条件下仍有很高的NOx选择性催化转化效率。温度对催化剂影响测试结果见图3。
实施例1
称取300g的Fe2O3,加入1200ml乙醇,加入纤维素0.5%,球磨2h得到A组分;100g的氧化铈、3000分子筛ZSM-5,加去离子水2000ml,加入氨水调节pH值至7~8,置于球磨罐,球磨2h;然后加入A组分,球磨2h得到铁基分子筛SCR催化剂原料,静置1h,105℃烘干,500℃烧结,研磨后得到粒径为2微米分子筛催化剂成品。
实施例2
称取300g氧化铜加入1200ml乙醇,加入纤维素0.5%,球磨2h得到A组分;100g的氧化铈、3000分子筛ZSM-5,加去离子水1200ml,加入氨水调节pH值至7,置于球磨罐,球磨2h;然后加入A组分,球磨2h得到铜基分子筛SCR催化剂原料,静置1h,105℃烘干,450℃烧结,研磨后得到粒径为1微米分子筛催化剂成品。
实施例3
称取300g氧化铜、100g氧化铁加入1200ml乙醇,加入纤维素0.5%,球磨2h得到A组分;100g的氧化铈、50g氧化镧、50g氧化锆以及3000的β分子筛,加去离子水1000ml,加入氨水调节pH值至7.5,置于球磨罐,球磨5h;然后加入A组分,球磨2h得到铜铁基分子筛SCR催化剂原料,静置1h,105℃烘干,550℃烧结,研磨后得到粒径为1微米分子筛催化剂成品。
实施例4
称取300g氧化铜加入1200ml乙醇,加入纤维素0.5%,球磨2h得到A组分;100g的氧化钛、100g氧化钒,100g氧化钨和3000分子筛ZSM-5,加去离子水1200ml,加入氨水调节pH值至7~9,置于球磨罐,球磨5h;然后加入A组分,球磨2h得到复合氧化物分子筛SCR催化剂原料,静置1h,105℃烘干,420℃烧结,研磨后得到分子筛催化剂成品。
实施例5
称取500g氧化铜,100g氧化铁加入1200ml乙醇,加入纤维素0.5%,球磨2h得到A组分;100g的氧化铈、50g氧化钴,50g氧化镍和3000分子筛MCM-41,加去离子水1000ml,加入氨水调节pH值至8~9,置于球磨罐,球磨3h;然后加入A组分,球磨2h得到复合氧化物分子筛SCR催化剂原料,静置1h,105℃烘干,500℃烧结,研磨后得到分子筛催化剂成品。
实施例6
称取500g氧化铜,100g氧化铁加入1200ml乙醇,加入纤维素0.5%,球磨2h得到A组分;100g的硝酸亚铈、150g硝酸锰,50g硝酸镧和3000分子筛SAPO-34,加去离子水1500ml,加入氨水调节pH值至7.5,置于球磨罐,球磨1h;然后加入A组分,球磨2h得到复合氧化物分子筛SCR催化剂原料,静置1h,105℃烘干,500℃烧结,研磨后得到分子筛催化剂成品。
实施例7
称取500g氧化铜,100g氧化铁加入1200ml乙醇,加入纤维素0.5%,球磨2h得到A组分;100g的硝酸亚铈、150g硝酸锰,50g硝酸铬和3000分子筛SSZ-13,加去离子水1500ml,加入氨水调节pH值至7.5,置于球磨罐,球磨1h;然后加入A组分,球磨2h得到复合氧化物分子筛SCR催化剂原料,静置1h,105℃烘干,500℃烧结,研磨后得到分子筛催化剂成品。
实施例8
称取300g氧化铜加入1200ml乙醇,加入纤维素0.5%,球磨2h得到A组分;100g的硝酸亚铈、50g硝酸锰,500g硝酸铜和3000分子筛SSZ-13,加去离子水2000ml,加入氨水调节pH值至7,置于球磨罐,球磨1h;然后加入A组分,球磨2h得到复合氧化物分子筛SCR催化剂原料,静置1h,105℃烘干,500℃烧结,研磨后得到分子筛催化剂成品。
实施例9
称取350g氧化铜加入1200ml乙醇,加入纤维素0.5%,球磨2h得到A组分;300g的硝酸亚铈、250g硝酸铁,500g硝酸铜、150g乙酸镍3500分子筛ZSM-5,,加去离子水1500ml,加入氨水调节pH值至7,置于球磨罐,球磨1h;然后加入A组分,球磨2h得到复合氧化物分子筛SCR催化剂原料,静置1h,105℃烘干,500℃烧结,研磨后得到分子筛催化剂成品。
Claims (1)
1.复合氧化物铁基分子筛SCR催化剂及其制备方法,其特征在于其制备方法,具体步骤如下:
(1)将铜、铁金属氧化物的一种或是两种加入球磨罐内,选择两种氧化时,氧化铜与氧化铁的比例为1:1~4:1,按料球比1:2投料,球直径为2mm~8mm,等份等比例添加直径不同的磨球,加入无水乙醇调和固体组分形成流动浆料,无水乙醇不需要比例,球磨得到A组分,球磨2~4h;
(2)将分子筛原料加水和分散剂材料乙醇球磨,分子筛:水:分散剂比例为2:1:1~4:2:1,按料球比1:2投料,球直径为2mm~8mm,等份等比例添加直径不同的磨球;
(3)在分子筛球磨罐内加入助催化剂金属盐化合物,稀土元素为La,Ce,Zr氧化物1%~10%;过渡金属为锰、钴、Ti、V、W、Cu、Cr、Ni元素的氧化物,可以是一种或是多种的混合,单一过渡元素添加量为1%~10%,两种以上时总添加量不大于10%,Mn:Co:Ti:V:W:Cu:Cr:Ni比例为1:1:1:1:1:1:1:1~2:1:1:0.5:1.5:2:1:2,由于测试数量限制,添加的材料也可以是此比例以外的组合配比,测试材料的pH值,使用氨水调节pH值至需要范围6~8,球磨1~2h;
(4)将A组分加入步骤(3)中,继续球磨2~6h,然后加入步骤(2)分子筛原料,继续球磨6~16h,然后得到含有催化剂元素的分子筛材料;
(5)含有催化剂元素的分子筛材料,经105℃脱水烘干、550℃煅烧、研磨后得到粒径为1~2微米的,去除氮氧化物的金属氧化物改性的分子筛SCR催化剂。
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CN113862719A (zh) * | 2021-11-05 | 2021-12-31 | 上海交通大学 | 一种过渡金属氧化物催化剂及其制备方法和应用 |
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