CN111346647B - Regular structure catalyst, preparation method and application thereof, and treatment method of incomplete regenerated flue gas - Google Patents
Regular structure catalyst, preparation method and application thereof, and treatment method of incomplete regenerated flue gas Download PDFInfo
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- CN111346647B CN111346647B CN201811577953.9A CN201811577953A CN111346647B CN 111346647 B CN111346647 B CN 111346647B CN 201811577953 A CN201811577953 A CN 201811577953A CN 111346647 B CN111346647 B CN 111346647B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 265
- 239000003546 flue gas Substances 0.000 title claims abstract description 117
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 202
- 239000002184 metal Substances 0.000 claims abstract description 188
- 238000000576 coating method Methods 0.000 claims abstract description 88
- 239000011248 coating agent Substances 0.000 claims abstract description 78
- 230000001603 reducing effect Effects 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 69
- 239000002243 precursor Substances 0.000 claims description 60
- 229910052799 carbon Inorganic materials 0.000 claims description 46
- 230000008929 regeneration Effects 0.000 claims description 44
- 238000011069 regeneration method Methods 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 32
- 239000011148 porous material Substances 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 22
- 239000006255 coating slurry Substances 0.000 claims description 21
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 238000002441 X-ray diffraction Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 238000004537 pulping Methods 0.000 claims description 9
- 229910001567 cementite Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052878 cordierite Inorganic materials 0.000 claims description 7
- 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 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052596 spinel Inorganic materials 0.000 claims description 6
- 239000011029 spinel Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 229910052664 nepheline Inorganic materials 0.000 claims description 3
- 239000010434 nepheline Substances 0.000 claims description 3
- 239000010451 perlite Substances 0.000 claims description 3
- 235000019362 perlite Nutrition 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 229910052845 zircon Inorganic materials 0.000 claims 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 28
- 150000004767 nitrides Chemical class 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 31
- 239000000395 magnesium oxide Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 229910020068 MgAl Inorganic materials 0.000 description 10
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 8
- 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 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000004231 fluid catalytic cracking Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000020477 pH reduction Effects 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
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- 238000001228 spectrum Methods 0.000 description 4
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 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 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 239000012692 Fe precursor Substances 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 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
- 238000004132 cross linking Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 238000004134 energy conservation Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001788 irregular Effects 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 nitrogen-containing compound Chemical class 0.000 description 1
- 229910001682 nordstrandite Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalytic cracking, and discloses a regular structure catalyst for reducing NOx emission in flue gas, a preparation method and application thereof, and a treatment method of incompletely regenerated flue gas, wherein the catalyst comprises the following components in parts by weight: the active component coating comprises an active metal component and a matrix, the active metal component comprises a first metal element, a second metal element and a third metal element, the first metal element comprises Fe and Co, and the weight ratio of Fe to Co is 1: (0.05-20), the second metal element is selected from at least one of group IA and/or IIA metal elements, and the third metal element is selected from at least one of non-noble metal elements in groups IB-VIIB. The catalyst provided by the invention has high catalytic conversion activity on reduced nitrides, is simple in preparation method, and can effectively reduce the emission of NOx in incompletely regenerated flue gas in catalytic cracking process when being used in the catalytic cracking process.
Description
Technical Field
The invention relates to the field of catalytic cracking, in particular to a regular structure catalyst for reducing NOx emission in flue gas, a preparation method and application thereof, and a treatment method of incompletely regenerated flue gas.
Background
The continuous rise of the price of the crude oil greatly increases the processing cost of a refinery, and the refinery reduces the cost by purchasing low-price inferior oil on one hand; on the other hand, the economic benefit is increased by deeply processing heavy oil. Catalytic cracking plays a major role in refineries as an important means for processing heavy oil in refineries, and is not only a main means for balancing heavy oil in refineries and producing clean fuel, but also an attention point for energy conservation and efficiency improvement of refineries. Catalytic cracking is a rapid catalytic reaction system with a catalyst rapidly deactivated, and the problem of catalyst regeneration is always the main line of catalytic cracking development.
In the process of Fluid Catalytic Cracking (FCC), raw oil and a regenerated catalyst are in rapid contact in a riser to carry out catalytic cracking reaction, coke generated by the reaction is deposited on the catalyst to cause the deactivation of the catalyst, the coke-formed deactivated catalyst enters a regenerator after being stripped and contacts with regenerated air or air rich in oxygen entering the bottom of the regenerator to carry out coke-burning regeneration. The regenerated catalyst is circulated back to the reactor to participate in the catalytic cracking reaction again. According to the content of the surplus oxygen in the flue gas in the regeneration process or the sufficient degree of CO oxidation, the catalytic cracking device can be divided into complete regeneration operation and incomplete regeneration operation.
In the complete regeneration process, the coke and the nitrogen-containing compounds in the coke generate CO under the action of regeneration air 2 And N 2 And also produces pollutants such as CO and NOx. The use of catalytic assistants being controlImportant technical measures for pollution of CO and NOx emissions.
An aid for controlling NOx emissions in flue gas regeneration fumes, commonly referred to as a NOx emission reduction aid or NOx reduction aid, for example CN102371150A discloses a non-precious metal composition for reducing NOx emissions in catalytic cracking regeneration fumes, said composition having a bulk ratio not exceeding 0.65 g/ml, based on the weight of said composition, containing, in terms of oxides: 50 to 99 weight percent of inorganic oxide carrier, (2) 0.5 to 40 weight percent of one or more non-noble metal elements selected from IIA, IIB, IVB and VIB groups, and (3) 0.5 to 30 weight percent of rare earth elements. The composition is used for fluidized catalytic cracking, and can remarkably reduce the emission of NOx in regeneration flue gas.
During incomplete regeneration, the flue gas from the regenerator outlet contains very low NOx and reduced nitrides such as NH due to low excess oxygen content and high CO concentration 3 And higher concentration of HCN and the like. These reduced nitrides flow downstream with the flue gas, and if they are sufficiently oxidized in the CO boiler for energy recovery, NOx is formed; if not sufficiently oxidized, residual NH 3 The ammonia nitrogen in the wastewater of the downstream washing tower exceeds the standard or is easy to cause the excess ammonia nitrogen and SO in the flue gas x The ammonium salt generated by the reaction is separated out to cause salt deposition of a waste boiler or other flue gas post-treatment equipment (such as SCR), and the long-period operation of the device is influenced. Thus, the incomplete regeneration process catalytically converts NH in the regenerator using a catalyst promoter 3 And the NOx emission in the flue gas can be reduced, and the operation period of the device is prolonged.
US5021144 discloses a method for reducing NH in flue gas of incomplete regeneration FCC device 3 The method of discharging is to add excess CO combustion improver into the regenerator in an amount 2-3 times the minimum addition to prevent lean bed afterburning. The method can reduce NH in flue gas of incomplete regeneration FCC device 3 But the emission is large, the energy consumption is high, and the environmental protection is not facilitated.
US4755282 discloses a process for reducing NH in flue gas of a partially or incompletely regenerated FCC unit 3 A method of venting. The method is characterized in that ammonia decomposition catalyst with the particle size of 10-40 mu m is added into a regeneratorAgent, keeping a certain concentration in the dilute phase bed layer, NH 3 Conversion to N 2 And water. The active component of the ammonia decomposition catalyst may be a noble metal dispersed on an inorganic oxide support.
CN101024179A discloses a NOx reducing composition for use in FCC processes comprising (i) an acidic metal oxide substantially free of zeolite, (ii) an alkali metal, an alkaline earth metal and mixtures thereof and (iii) an oxygen storage component. The prepared composition is impregnated by noble metal to convert gas phase reduced nitrogen substances in the flue gas of an incomplete regeneration catalytic cracking unit and reduce the emission of NOx in the flue gas.
Currently, for controlling the flue gas NH of incomplete regenerators 3 And NOx emission catalyst technology research and application reports are relatively few, and because the difference between the smoke composition of an incomplete regeneration device and a complete regeneration device is obvious, the existing catalytic auxiliary agent applicable to the complete regeneration device has an undesirable application effect on the incomplete regeneration device. The auxiliary agent composition disclosed in the technology can catalyze and convert NH in the flue gas to a certain extent 3 Nitride in reduced state, but for NH in flue gas 3 The catalytic conversion activity of the nitride in reduced state is still to be improved to slow down NH 3 And the influence of deposited salt on the operation of equipment is avoided, so that a flue gas pollutant emission reduction catalyst system suitable for an incomplete regeneration device needs to be developed, and the emission of flue gas NOx is further reduced.
Disclosure of Invention
Aiming at NH in the regeneration process, particularly in the incomplete regeneration process in the prior art 3 The invention provides a regular structure catalyst for reducing NOx emission in flue gas, a preparation method and application thereof, and a treatment method of incompletely regenerated flue gas. The regular structure catalyst for reducing NOx emission in flue gas provided by the invention has high catalytic conversion activity on reduced nitrides, is simple in preparation method, and can effectively reduce NOx emission in incompletely regenerated flue gas in catalytic cracking process.
In order to achieve the above object, a first aspect of the present invention provides a structured catalyst for reducing NOx emission in flue gas, the catalyst comprising: the catalyst comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier, wherein the content of the active component coating is 10-50 wt% based on the total weight of the catalyst; the active component coating contains an active metal component and a substrate, the active metal component comprises a first metal element, a second metal element and a third metal element, the first metal element is selected from a VIII group non-noble metal element, the first metal element comprises Fe and Co, and the weight ratio of Fe to Co is 1: (0.05-20), the second metal element is selected from at least one of group IA and/or IIA metal elements, and the third metal element is selected from at least one of group IB-VIIB non-noble metal elements.
Preferably, the weight ratio of Fe to Co, calculated as oxides, is 1: (0.1-10), preferably 1: (0.3-3), more preferably 1: (0.5-2), most preferably 1: (0.6-1).
In a second aspect, the present invention provides a method for preparing a structured catalyst for reducing NOx emissions in flue gases, the method comprising:
(1) Mixing and pulping a substrate source, a first metal element precursor, a second metal element precursor, a third metal element precursor and water to obtain active component coating slurry;
(2) Coating a regular structure carrier with the active component coating slurry, and drying and roasting to obtain an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier;
the first metal element is selected from VIII group non-noble metal elements, the first metal element comprises Fe and Co, the second metal element is selected from at least one of IA group metal elements and/or IIA group metal elements, and the third metal element is selected from at least one of IB-VIIB group non-noble metal elements;
in the first metal element precursor, the use amounts of the precursor of Fe and the precursor of Co are such that the weight ratio of Fe to Co in the prepared catalyst is 1: (0.05-20).
According to a third aspect of the present invention, there is provided a structured catalyst for reducing NOx emissions in flue gases made by the above method.
According to a fourth aspect of the present invention, there is provided the use of the above structured catalyst for reducing NOx emissions in flue gas in catalytic cracking incompletely regenerated flue gas treatment.
According to a fifth aspect of the present invention, there is provided a method for treating incomplete regeneration flue gas, the method comprising: the incompletely regenerated flue gas is contacted with a catalyst, and the catalyst is the regular structure catalyst for reducing the emission of NOx in the flue gas.
Preferably, the contacting is performed in a flue gas channel provided in front of the CO incinerator and/or the CO incinerator, further preferably in a flue gas channel provided in front of the CO incinerator.
Compared with the prior art, the regular structure catalyst for reducing the NOx emission in the flue gas provided by the invention has the following technical effects:
(1) In the regular structure catalyst, the specific kind of active components are distributed on the inner/outer surface of the regular structure catalyst in a coating mode, the dispersion degree of active metals in the coating is higher, and the catalyst has high activity on NH 3 The catalytic conversion activity of the nitride in the reduced state is obviously improved;
(2) The method for treating the incompletely regenerated flue gas can effectively reduce the emission of NOx in the incompletely regenerated flue gas by adopting the catalyst with the regular structure, and preferably, the catalyst and the incompletely regenerated flue gas are carried out in a flue gas channel arranged in front of a CO incinerator and/or a CO incinerator, and further preferably carried out in a flue gas channel arranged in front of the CO incinerator, so that NH is more favorably treated 3 The catalytic conversion activity of the reduced nitrides is improved, and the distribution of FCC products is not influenced at all.
Drawings
FIG. 1 is an XRD pattern of the structured catalyst for reducing NOx emissions in flue gas prepared in examples 1 and 4.
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 numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
In the present invention, the term "structured catalyst" is used to mean a catalyst comprising a structured carrier and a coating of an active component distributed on the inner and/or outer surface of the carrier; a "regular structure vector" is a vector having a regular structure.
In a first aspect, the present invention provides a structured catalyst for reducing NOx emissions in flue gas, the catalyst comprising: the catalyst comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier, wherein the content of the active component coating is 10-50 wt% based on the total weight of the catalyst; the active component coating contains an active metal component and a substrate, the active metal component comprises a first metal element, a second metal element and a third metal element, the first metal element is selected from a VIII group non-noble metal element, the first metal element comprises Fe and Co, and the weight ratio of Fe to Co is 1: (0.05-20), the second metal element is selected from at least one of group IA and/or IIA metal elements, and the third metal element is selected from at least one of group IB-VIIB non-noble metal elements.
In the regular structure catalyst provided by the invention, active components, namely a first metal element (comprising Fe and Co), a second metal element and a third metal element exist on the inner surface and/or the outer surface of a regular structure carrier in the form of an active metal component coating, the active metal in the coating has high dispersity, and the active metal has high dispersity on NH 3 The catalytic conversion activity of the nitride in the reduced state is obviously improved.
According to a preferred embodiment of the present invention, the active component coating is present in an amount of 15 to 40 wt. -%, preferably 20 to 35 wt. -%, most preferably 20 to 30 wt. -%, based on the total weight of the catalyst.
According to the structured catalyst provided by the invention, preferably, the content of the matrix is 10-90 wt% based on the total weight of the active component coating, and the content of the first metal element is 0.5-50 wt%, the content of the second metal element is 0.5-20 wt%, and the content of the third metal element is 0.5-20 wt% calculated by oxide.
Further preferably, the content of the substrate is 50 to 90 wt%, the content of the first metal element is 3 to 30 wt%, the content of the second metal element is 1 to 20 wt%, and the content of the third metal element is 1 to 10 wt%, calculated as an oxide, based on the total weight of the active component coating.
Still more preferably, the content of the substrate is 55 to 85 wt%, the content of the first metal element is 5 to 25 wt%, the content of the second metal element is 5 to 15 wt%, and the content of the third metal element is 2 to 8 wt%, calculated as an oxide, based on the total weight of the active component coating layer.
Most preferably, the content of the substrate is 66-85 wt%, the content of the first metal element is 6-16 wt%, the content of the second metal element is 5-12 wt%, and the content of the third metal element is 3-8 wt%, calculated as oxide, based on the total weight of the active component coating.
In the invention, the contents of all components in the catalyst with the regular structure are measured by adopting an X-ray fluorescence spectrum analysis method (a petrochemical engineering analysis method (RIPP experimental method), compilation of Yangcui and the like, published by scientific publishing company in 1990).
The first metal element comprises Fe and Co, and the invention does not exclude that the first metal element also comprises elements other than Fe and Co in the VIII group non-noble metal elements, such as Ni.
In the present invention, the first metal element may contain Fe and Co as long as it can increase NH content of the catalyst 3 In order to further exhibit the synergistic effect of Fe and Co, the catalytic conversion activity of the reduced nitrides is preferably such that the weight ratio of Fe to Co, calculated as oxides, is 1: (0.1-10), further preferablyThe ratio of 1 (0.3-3), more preferably 1: (0.5-2), most preferably 1: (0.6-1).
In the present invention, unless otherwise specified, fe in terms of oxide means Fe in terms of Fe 2 O 3 In terms of Co as oxide, co means Co as Co 2 O 3 And (6) counting.
According to a preferred embodiment of the invention, the Fe in the catalyst is at least partly present in the form of iron carbide, preferably Fe 3 C and/or Fe 7 C 3 . The amount of iron carbide present is not particularly limited in the present invention, and the performance of the structured catalyst can be effectively improved as long as part of the iron carbide is present.
According to a preferred embodiment of the invention, the Co of the catalyst is at least partly present in the form of elemental cobalt. The invention has no special limitation on the existing amount of the simple substance cobalt, and the performance of the regular structure catalyst can be effectively improved as long as part of the simple substance cobalt is present.
It should be noted that the prior art provides catalysts in which the metal element is mostly present in the form of oxidation state. In the preparation process of the catalyst, a roasting mode is preferably adopted under a carbon-containing atmosphere, so that part of FeO is converted into iron carbide, and part of CoO is converted into simple substance cobalt. The inventor of the invention finds that the existence of the iron carbide and/or the simple substance cobalt can enable the catalyst to better promote the decomposition of the nitrogen-containing compound in a reduction state, reduce the generation of nitrogen oxides and promote the reduction of the nitrogen oxides to a certain extent.
According to the regular structure catalyst provided by the invention, preferably, the XRD pattern of the catalyst has diffraction peaks at 42.6 degrees, 44.2 degrees and 44.9 degrees of 2 theta.
Specifically, the diffraction peaks for iron carbide at 42.6 ° and 44.9 ° 2 θ; the diffraction peak of the simple substance cobalt is at 44.2 degrees in the 2 theta.
According to a preferred embodiment of the present invention, the catalyst provided by the present invention has an XRD pattern in which the diffraction peak at 44.9 ° 2 θ is stronger than the diffraction peak at 42.6 ° 2 θ.
In the invention, the structured catalyst adopts an X-ray diffractometer (Siemens company D5005 type) to obtain an XRD spectrogram and carries out structure determination, and the specific conditions comprise: cu target, ka radiation, solid detector, tube voltage 40kV, tube current 40mA.
In the present invention, the group IA metal elements include, but are not limited to, na and/or K; the group IIA metal element includes, but is not limited to, at least one of Mg, ca, sr, and Ba. In the invention, the non-noble metal elements in groups IB-VIIB refer to non-noble metals from groups IB to VIIB in the periodic table of elements, including non-noble metals in groups IB, metals in groups IIB, metals in groups IIIB, metals in groups IVB, metals in groups VB, metals in groups VIB and metals in groups VIIB, specifically, the non-noble metal elements in groups IB-VIIB include but are not limited to at least one of Cu, zn, cd, sc, Y, ti, zr, V, nb, cr, mo, W, mn, re and rare earth elements; the rare earth elements include, but are not limited to, at least one of La, ce, pr, nd, pm, sm, and Eu.
According to the structured catalyst provided by the present invention, preferably, the second metal element is at least one selected from Na, K, mg and Ca, more preferably K and/or Mg, and most preferably Mg.
According to the structured catalyst provided by the present invention, the third metal element is preferably at least one selected from Cu, zn, ti, zr, V, cr, mo, W, mn and rare earth elements, preferably at least one selected from Zr, V, W, mn, ce and La, and most preferably Mn.
According to a most preferred embodiment of the present invention, the NH content of the catalyst with a regular structure can be greatly increased by using Fe, co, mg and Mn as active components 3 The catalytic conversion activity of the reduced nitrides is equal, and the regular structure catalyst has more excellent hydrothermal stability.
According to a most preferred embodiment of the present invention, the catalyst comprises: the catalyst comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier, wherein the content of the active component coating is 10-50 wt% based on the total weight of the catalyst; the active component coating contains Fe, co, mg, mn and alumina, and the weight ratio of Fe to Co is 1: (0.5-2), based on the total weight of the active component coating, the content of the aluminum oxide is 66-85 wt%, the total content of Fe and Co is 6-16 wt%, the content of Mg is 5-12 wt%, and the content of Mn is 3-8 wt%.
According to the regular structure catalyst provided by the invention, preferably, the matrix is at least one selected from alumina, silica-alumina, zeolite, spinel, kaolin, diatomite, perlite and perovskite, preferably at least one selected from alumina, spinel and perovskite, and further preferably alumina.
The structured catalyst according to the invention, wherein the structured carrier can be used in a catalyst bed provided in a fixed bed reactor. The regular structure carrier can be a whole carrier block, a hollow pore channel structure is formed inside the regular structure carrier, a catalyst coating can be distributed on the inner wall of a pore channel, and the pore channel space can be used as a flowing space of fluid. Preferably, the structured carrier is selected from a monolithic carrier having a parallel channel structure with two open ends. The structured carrier can be a honeycomb structured carrier (honeycomb carrier for short) with honeycomb open pores on the cross section.
According to the structured catalyst of the present invention, the structured carrier preferably has a pore density of 20 to 900 pores per square inch, preferably 20 to 300 pores per square inch, in cross section; the open porosity of the cross section of the carrier with the regular structure is 20-80%, preferably 50-80%. The holes can be regular or irregular, and the holes can be the same or different in shape and can be independent of each other in a square shape, a regular triangle shape, a regular hexagon shape, a circular shape or a corrugated shape.
According to the structured catalyst of the present invention, preferably, the structured carrier may be at least one selected from the group consisting of a cordierite honeycomb carrier, a mullite honeycomb carrier, a diamond honeycomb carrier, a corundum honeycomb carrier, a zirconia corundum honeycomb carrier, a quartz honeycomb carrier, a nepheline honeycomb carrier, a feldspar honeycomb carrier, an alumina honeycomb carrier, and a metal alloy honeycomb carrier.
In a second aspect, the present invention provides a method for preparing a structured catalyst for reducing NOx emissions in flue gases, the method comprising:
(1) Mixing and pulping a substrate source, a first metal element precursor, a second metal element precursor, a third metal element precursor and water to obtain active component coating slurry;
(2) Coating a regular structure carrier with the active component coating slurry, and drying and roasting to obtain an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier;
the first metal element is selected from non-noble metal elements in a group VIII, the first metal element comprises Fe and Co, the second metal element is selected from at least one of metal elements in a group IA and/or IIA, and the third metal element is selected from at least one of non-noble metal elements in a group IB-VIIB;
in the first metal element precursor, the use amounts of the precursor of Fe and the precursor of Co are such that, in the prepared catalyst, the weight ratio of Fe to Co is 1: (0.05-20).
In the present invention, specifically, the matrix source is a substance that can be converted into a matrix under the conditions of the firing in step (2). The present invention is not particularly limited in this regard. The kind of the substrate is as described above, and is not described in detail herein. When the substrate is preferably alumina, the substrate source may be a precursor to alumina, for example the substrate source is selected from at least one of gibbsite, surge dawsonite, nordstrandite, diaspore, boehmite and pseudoboehmite, most preferably pseudoboehmite.
According to the method provided by the invention, preferably, before pulping, the matrix source is subjected to acidification peptization treatment, wherein the acidification peptization treatment can be carried out according to the conventional technical means in the field, and further preferably, the acid used in the acidification peptization treatment is hydrochloric acid.
The selection range of the acidification peptization conditions is wide, and preferably, the acidification peptization conditions comprise: the acid-aluminum ratio is 0.12-0.22:1, the time is 10-40min.
In the present invention, the aluminum acid ratio refers to a mass ratio of hydrochloric acid calculated as 36 wt% of concentrated hydrochloric acid to a precursor of alumina on a dry basis, unless otherwise specified.
According to the present invention, the first metal element precursor, the second metal element precursor, and the third metal element precursor are respectively selected from water-soluble salts of the first metal element, the second metal element, and the third metal element, such as nitrate, chloride, chlorate, sulfate, and the like, and the present invention is not particularly limited thereto.
According to the method provided by the present invention, the regular structure carrier and the first metal element, the second metal element and the third metal element are selected as described above, and are not described herein again.
In the present invention, preferably, the solid content of the active component coating slurry of step (1) is 8 to 30% by weight.
According to the method provided by the present invention, there is no particular limitation on the method for mixing and pulping the substrate source, the first metal element precursor, the second metal element precursor, the third metal element precursor and water, and the order of adding the substrate source, the first metal element precursor, the second metal element precursor and the third metal element precursor is also not limited as long as the substrate source, the first metal element precursor, the second metal element precursor and the third metal element precursor are contacted with water, preferably, the first metal element precursor and the third metal element precursor are dissolved in water first, then the substrate source (preferably, an acidified substrate source) is added to obtain a first solution, the second metal element precursor is mixed with water to obtain a second solution, finally, the first solution and the second solution are mixed, and then pulping is performed to obtain a slurry.
In the invention, the roasting can effectively improve the NH of the catalyst with the regular structure by adopting the conventional technical means in the field 3 The catalytic conversion activity of the reduced nitrides is equal, but in order to further increase the NH of the catalysts with regular structures 3 The catalytic conversion activity and hydrothermal stability of the nitride in an isoreduced state, and preferably the calcination is carried out in a carbon-containing atmosphere. The inventors of the present invention have unexpectedly found in the course of their research that the calcination is carried out in a carbon-containing atmosphereThe method can make the catalyst with a regular structure to react with NH 3 The catalytic conversion activity and the hydrothermal stability of the nitride in the reduced state are both obviously improved. The improvement of activity may be related to the conversion of the active components from oxides to carbides and to reduction, while the improvement of hydrothermal stability may be related to the fact that the high temperature treatment further promotes the adhesion, fusion and crosslinking of the active components in the catalyst. It can be seen from the XRD contrast spectrum that the obvious iron carbide peak pattern and the peak pattern of the simple substance cobalt appear after the treatment. Specifically, as shown in FIG. 1, the XRD pattern of the regular structure catalyst S-4 which has not been treated with the carbon-containing atmosphere has a diffraction peak of MgO at about 43.0 degrees and Al at about 45.0 degrees 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 The XRD spectrum of the regular structure catalyst S-1 treated by the carbon-containing atmosphere has a diffraction peak of MgO at about 43.0 degrees and Al at about 45.0 degrees 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 And the diffraction peaks at about 43.0 degrees and about 45.0 degrees are obviously strengthened and shifted to the left, and due to the fact that the catalyst S-1 with the regular structure is treated by the carbon-containing atmosphere, the diffraction peaks appear at 42.6 degrees and 44.9 degrees of 2 theta, and the diffraction peaks at 42.6 degrees and 44.9 degrees of 2 theta are FeC (Fe) 3 C and Fe 7 C 3 ) The diffraction peak of (1). In addition, compared with the regular structure catalyst S-4, the regular structure catalyst S-1 has a diffraction peak at 44.2 degrees, and the diffraction peak at 44.2 degrees 2 theta is the diffraction peak of simple substance cobalt.
It should be noted that FIG. 1 shows only XRD patterns in the range of 41 to 50, which is mainly used to illustrate the presence of Fe and Co in the structured catalyst. Outside the range of 41 ° to 50 °, there are other diffraction peaks, for example, diffraction peaks of FeO (at 37 °, 65 ° and 59 ° for 2 θ) and CoO (at 37 °, 65 ° and 31 ° for 2 θ), which are not further explained in the present invention.
According to a preferred embodiment of the present invention, the conditions of the calcination include: under a carbon-containing atmosphere, at a temperature of 400-1000 ℃, preferably 450-650 ℃, for 0.1-10h, preferably 1-3h.
In the present invention, the pressure for the calcination is not particularly limited, and the calcination may be carried out under normal pressure. For example, it can be carried out at 0.01 to 1MPa (absolute pressure).
In the present invention, the carbon-containing atmosphere is provided by a gas containing a carbon-containing element, and the carbon-containing gas is preferably selected from gases containing a carbon-containing element having reducing properties, further preferably at least one of CO, methane and ethane, and most preferably CO.
According to the present invention, the gas containing the carbon-containing element may further contain a part of an inert gas, and the inert gas may be any of various inert gases conventionally used in the art, and preferably the inert gas is selected from at least one of nitrogen, argon, and helium, and further preferably nitrogen.
According to a preferred embodiment of the present invention, the carbon-containing atmosphere is provided by a mixed gas containing CO and nitrogen, and the volume concentration of CO in the carbon-containing atmosphere is preferably 1 to 20%, and more preferably 4 to 10%. By adopting the preferred embodiment of the invention, the treatment requirements can be better met, and the safety of operators can be ensured.
In the present invention, the calcination may be performed in a calciner, which may be a rotary calciner used in the production of catalytic cracking catalysts and promoters. The gas containing carbon element is in countercurrent contact with the solid material in the roasting furnace.
The drying conditions in step (2) are not particularly limited in the present invention, and may be performed according to the conventional techniques in the art, for example, the drying conditions in step (2) may include: the temperature is 60-150 ℃ and the time is 2-10h.
According to the method of the present invention, preferably, the coating is performed such that the content of the active component coating layer in the prepared catalyst is 10 to 50 wt%, preferably 15 to 40 wt%, further preferably 20 to 35 wt%, and most preferably 20 to 30 wt%, based on the total amount of the catalyst. On the basis of the content, the content of the active component coating can be adjusted by controlling parameters in the coating process by the skilled person, for example, the amount of the active component coating slurry and the structured carrier in the coating process.
The coating in the method provided by the invention can be realized by coating the active component coating slurry on the inner surface and/or the outer surface of the regular structure carrier by adopting various coating methods; the coating method may be a water coating method, a dipping method or a spraying method. The specific operation of coating can be carried out with reference to the method described in CN 1199733C. In a preferable case, the coating is carried out by a water coating method, one end of the regular structure carrier is immersed in the active component coating slurry in the coating process, and vacuum is applied to the other end of the regular structure carrier, so that the active component coating slurry continuously passes through the pore channels of the regular structure carrier. The volume of the active component coating slurry passing through the pore channel of the regular structure carrier can be 2-20 times of the volume of the regular structure carrier, the applied vacuum pressure can be-0.1 MPa (MPa) to-0.01 MPa (MPa), the coating temperature can be 10-70 ℃, and the coating time can be 0.1-300 seconds. And drying the regular structure carrier coated with the active component coating slurry to obtain the active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier.
The selection range of the use amounts of the matrix source, the first metal element precursor, the second metal element precursor and the third metal element precursor is wide, and preferably, the use amounts of the matrix source, the first metal element precursor, the second metal element precursor and the third metal element precursor are such that, in the prepared catalyst, based on the total weight of the active component coating, the content of the matrix is 10 to 90 wt%, the content of the first metal element is 0.5 to 50 wt%, the content of the second metal element is 0.5 to 20 wt%, and the content of the third metal element is 0.5 to 20 wt%; preferably, the content of the substrate is 50-90 wt%, the content of the first metal element is 3-30 wt%, the content of the second metal element is 1-20 wt%, and the content of the third metal element is 1-10 wt% calculated by oxide, based on the total weight of the active component coating; further preferably, the content of the substrate is 55 to 85 wt%, the content of the first metal element is 5 to 25 wt%, the content of the second metal element is 5 to 15 wt%, and the content of the third metal element is 2 to 8 wt% in terms of oxide, based on the total weight of the active component coating; most preferably, the content of the substrate is 66-85 wt%, the content of the first metal element is 6-16 wt%, the content of the second metal element is 5-12 wt%, and the content of the third metal element is 3-8 wt%, calculated as oxide, based on the total weight of the active component coating.
According to the method provided by the invention, preferably, the mass ratio of the used amount of the substrate source calculated by oxides, the first metal element precursor calculated by the VIII group non-noble metal element oxide, the second metal element precursor calculated by the IA and/or IIA group metal element oxide and the third metal element precursor calculated by the IB-VIIB group non-noble metal element oxide is 10-90:0.5-50:0.5-20:0.5-20; further, it may be 50 to 90:3-30:1-20:1-10; still further, it may be 55-85:5-25:5-15:2-8, and can also be 66-85:6-16:5-12:3-8.
According to a preferred embodiment of the present invention, the Fe precursor and the Co precursor are used in amounts such that, in the resulting catalyst, the weight ratio of Fe to Co, calculated as oxides, is preferably 1: (0.1 to 10), more preferably 1 (0.3 to 3), still more preferably 1: (0.5-2), most preferably 1: (0.6-1).
In a third aspect, the invention provides a structured catalyst prepared by the method for reducing NOx emission in flue gas. The catalyst comprises: the catalyst comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier, wherein the content of the active component coating is 10-50 wt% based on the total weight of the catalyst; the active component coating contains an active metal component and a substrate, the active metal component comprises a first metal element, a second metal element and a third metal element, the first metal element is selected from a VIII group non-noble metal element, the first metal element comprises Fe and Co, and the weight ratio of Fe to Co is 1: (0.05-20), the second metal element is selected from at least one of group IA and/or IIA metal elements, and the third metal element is selected from at least one of group IB-VIIB non-noble metal elements. The structured catalyst prepared by the method of the present invention has the same technical features as the structured catalyst claimed in the present invention, and the specific contents refer to the previous description of the structured catalyst of the present invention.
The regular structure catalyst for reducing NOx emission in flue gas provided by the invention is suitable for various working conditions, the catalytic conversion activity of reduced nitride is high, the hydrothermal stability is good, the preparation method is simple, and the regular structure catalyst is used in a catalytic cracking process and can effectively reduce the NOx emission in incompletely regenerated flue gas of catalytic cracking. Therefore, the fourth aspect of the present invention provides the use of the above structured catalyst for reducing NOx emissions in flue gas in the treatment of catalytic cracking incompletely regenerated flue gas.
The fifth aspect of the invention provides a method for treating incomplete regeneration flue gas, which comprises the following steps: the incomplete regeneration flue gas is contacted with a catalyst, and the catalyst is a regular structure catalyst for reducing the emission of NOx in the incomplete regeneration flue gas.
The composition of the incomplete regeneration flue gas is not particularly limited, and the incomplete regeneration flue gas can be obtained by an incomplete regeneration catalytic cracking unit, preferably, the incomplete regeneration flue gas contains O 2 Is not more than 0.1% by volume, CO is not less than 4% by volume, NH 3 Is not less than 200ppm and the NOx content is not more than 10ppm. During incomplete regeneration, the flue gas from the regenerator has a very low NOx concentration and reduced nitrides such as NH due to low excess oxygen content and high CO concentration 3 And higher concentration of HCN and the like. These reduced nitrides flow downstream along with the flue gas, and are sufficiently oxidized in the CO incinerator for energy recovery, resulting in the formation of NOx. In this connection, it is preferred that said contacting of the incompletely regenerated flue gas with the catalyst is carried out in the CO incinerator and/or in a flue gas channel arranged in front of the CO incinerator, i.e. before the reduced nitrides are oxidized, they are removed. In a CO incinerator, air supply is usually performed, and reduced nitrogen is easily oxidized to form NOx without using a catalyst, in order to prevent the reduced nitrogenThe oxide is oxidized, preferably, when the contacting is carried out in a CO incinerator, preferably, the contacting is at the front of the CO incinerator. Most preferably, the contact between the incompletely regenerated flue gas and the catalyst is carried out in a flue gas channel arranged in front of the CO incinerator, namely, the catalyst is placed in the flue gas channel arranged in front of the CO incinerator, the incompletely regenerated flue gas is in an oxygen-deficient state in the flue gas channel, and the contact between the incompletely regenerated flue gas and the catalyst in the flue gas channel is more favorable for NH 3 Catalytic conversion of the iso-reduced nitrides.
The catalyst for incompletely regenerated flue gas provided in the prior art exists in a fluidized bed layer of a catalytic cracking regenerator in the form of catalyst promoter microspheres, and the flue gas is fully contacted with the catalyst to realize the effect of reducing NOx emission.
In the present invention, the ppm refers to a volume concentration unless otherwise specified.
The CO incinerator is not particularly limited, and various types of CO incinerators conventionally used in the art, such as a vertical type CO incinerator or a horizontal type CO incinerator, may be used.
According to the present invention, preferably, the conditions of the contacting include: the temperature is 600-1000 ℃, the gauge pressure is measured, the reaction pressure is 0-0.5MPa, and the mass space velocity of the flue gas is 10-1000h -1 Further preferably, the contacting conditions include: the temperature is 650-850 ℃, the reaction pressure is 0.1-0.3MPa, and the mass space velocity of the flue gas is 30-500h -1 . In the present invention, the flue gas mass space velocity is not particularly limited, and is measured relative to the active component coating of the structured catalyst, that is, the mass of flue gas passing through the active component coating per mass per unit time.
Preferably, the structured catalyst is present in the form of a catalyst bed. In the method for treating the incompletely regenerated flue gas, the regular structure catalyst can be used as a fixed catalyst bed layer to be arranged in a flue gas channel arranged in front of a CO incinerator and/or a CO incinerator, and the flowing incompletely regenerated flue gas can flow through the regular structure catalyst bed layer, namely can flow through a pore channel in a regular structure carrier and react with an active component coating distributed on the wall of the pore channel.
According to the method provided by the invention, an energy recovery process can be further included, the energy recovery process can be carried out according to conventional technical means in the field, and specifically, partial catalyst fine powder carried by incomplete regeneration flue gas obtained by an incomplete regeneration catalytic cracking device is separated by a cyclone separator (preferably sequentially passing through a secondary cyclone separator and a tertiary cyclone separator), and then the incomplete regeneration flue gas is sent to a flue gas turbine, the flue gas turbine is connected with a main fan, the flue gas turbine expands to do work to drive the main fan to recover pressure energy and heat energy in the incomplete regeneration flue gas, and the incomplete regeneration flue gas after energy recovery by the flue gas turbine is sent to a CO incinerator.
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
The contents of the components in the structured catalyst for reducing NOx emission in flue gas in the following examples were measured by X-ray fluorescence spectroscopy (XRF), which is specifically described in the editions of petrochemical analysis (RIPP test), yancui, and the like, published by the scientific press in 1990.
In the examples, the structured catalyst for reducing NOx emission in flue gas is subjected to structure measurement by using an X-ray diffractometer (Siemens corporation, model D5005), and an XRD spectrogram is obtained, specifically: taking 1g of the active component coating on the outer surface of the catalyst with the regular structure, grinding the coating to be used as a sample, cu target, kalpha radiation, a solid detector, tube voltage 40kV and tube current 40mA.
The raw materials used in the examples and comparative examples: cobalt nitrate [ Co (NO) 3 ) 2 ·6H 2 O]For analytical purity, ferric nitrate [ Fe (NO) 3 ) 3 ·9H 2 O]For analytical purification, potassium permanganate [ KMnO ] 4 ]For analytical purity, magnesium oxide [ MgO]For analytical purification, it is produced by chemical reagents of the national drug group; pseudo-boehmite is an industrial grade product, the content of alumina is 64 weight percent, and the pore volume is 0.31 ml/g, which is produced by Shandong aluminum company; hydrochloric acid, concentration 36.5% by weight, analytically pure,production in Beijing chemical plant; carbon monoxide with a concentration of 10 vol%, nitrogen as a balance gas, produced by Beijing helium Pubei gas industries, ltd.
The coating method in the following examples and comparative examples is a water coating method, and the specific process method comprises the following steps: in each coating process, one end of the regular structure carrier is immersed in the active component coating slurry, and the other end of the regular structure carrier is vacuumized, so that the active component coating slurry continuously passes through the pore channel of the regular structure carrier; the vacuum pressure applied was-0.03 MPa (MPa) and the temperature of coating was 35 ℃.
Example 1
(1) Adding 262g of pseudo-boehmite into 1.42kg of deionized water, pulping and dispersing, then adding 23.8mL of hydrochloric acid, acidifying for 15min to obtain aluminum-aluminum colloid, and adding ferric nitrate (calculated as Fe) calculated by metal oxide 2 O 3 Calculated as Co) 6g, cobalt nitrate (calculated as Co) 2 O 3 Meter) 6g, KMnO 4 Adding 10g (calculated by MnO) of the aluminum-based composite material into 350mL of water, stirring until the aluminum-based composite material is fully dissolved, adding the aluminum-based composite material into the mixture, and stirring for 15min to obtain a first solution; adding 10g of MgO into 30g of water, stirring for 10min, adding into the first solution, and stirring for 20min to obtain active component coating slurry;
(2) Coating a cordierite honeycomb carrier (the carrier has a pore density of 400 pores/square inch, an open pore ratio of a cross section of 70% and a square shape) with the active component coating slurry obtained in the step (1), drying (100 ℃,4 hours), transferring the carrier into a tube furnace, and introducing CO/N having a CO concentration of 10 vol% at a flow rate of 100mL/min 2 And treating the mixed gas at 600 ℃ for 1.5h to obtain an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier to obtain the regular structure catalyst S-1, wherein the content of the active component coating is 25 wt% based on the total weight of the regular structure catalyst.
The measurement results of the contents of the components in the active component coating of the catalyst S-1 with the regular structure are shown in Table 1.
XRD analysis was performed on the regular structure catalyst S-1, and the XRD spectrum was as shown in FIG. 1, and it can be seen from FIG. 1 that the regular structure catalyst S-4 which had not been subjected to the carbon-containing atmosphere treatment had a diffraction of MgO at about 43.0 degreePeak, al at about 45.0 ° 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 The XRD spectrum of the regular structure catalyst S-1 treated by the carbon-containing atmosphere has a diffraction peak of MgO at about 43.0 degrees and Al at about 45.0 degrees 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 And the diffraction peaks at about 43.0 degrees and about 45.0 degrees are obviously strengthened and shifted to the left, and due to the fact that the catalyst S-1 with the regular structure is treated by the carbon-containing atmosphere, the diffraction peaks appear at 42.6 degrees and 44.9 degrees of 2 theta, and the diffraction peaks at 42.6 degrees and 44.9 degrees of 2 theta are FeC (Fe) 3 C and Fe 7 C 3 ) The diffraction peak of (4). In addition, compared with the regular structure catalyst S-4, the regular structure catalyst S-1 has a diffraction peak at 44.2 degrees, and the diffraction peak at 44.2 degrees 2 theta is the diffraction peak of simple substance cobalt.
It should be noted that FIG. 1 shows only XRD patterns in the range of 41 to 50, which is mainly used to illustrate the presence of Fe and Co in the structured catalyst. Outside the range of 41-50 degrees, other diffraction peaks exist, for example, diffraction peaks of FeO (2 theta is at 37 degrees, 65 degrees and 59 degrees) and CoO (2 theta is at 37 degrees, 65 degrees and 31 degrees), and diffraction peaks outside the range of 41-50 degrees are not related to diffraction peaks of FeC and simple substance Co, and the invention does not carry out further spectrum analysis.
Example 2
(1) Adding 253g of pseudo-boehmite into 1.37kg of deionized water for pulping and dispersing, then adding 22.9mL of hydrochloric acid for acidification for 15min to obtain an aluminum-aluminum colloid, and adding ferric nitrate (calculated as Fe) calculated as metal oxide 2 O 3 Calculated as Co) 10g, cobalt nitrate (calculated as Co) 2 O 3 Meter) 6g, KMnO 4 Adding 6g (calculated by MnO) into 350mL of water, stirring until the mixture is fully dissolved, adding the aluminum colloid into the mixture, and stirring for 15min to obtain a first solution; adding 16g of MgO into 48g of water, stirring for 10min, adding into the first solution, and stirring for 20min to obtain active component coating slurry;
(2) Coating a cordierite honeycomb carrier (the carrier has a pore density of 400 pores per square inch, an open pore ratio of 70% in cross section, and a square pore shape) with the active component coating slurry obtained in the step (1)Form), dried (100 ℃ C., 4 hours), then transferred to a tube furnace, and CO/N was introduced at a CO concentration of 10 vol% at a flow rate of 100mL/min 2 And treating the mixed gas at 500 ℃ for 3h to obtain an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier to obtain the regular structure catalyst S-2, wherein the content of the active component coating is 30 wt% based on the total weight of the regular structure catalyst.
The measurement results of the contents of the components in the active component coating of the catalyst S-2 with the regular structure are shown in Table 1.
XRD analysis of the regular structure catalyst S-2 was similar to that of example 1. In XRD spectrogram of regular structure catalyst S-2 treated by carbon-containing atmosphere, there are not only MgO diffraction peak around 43.0 degrees, but also Al around 45.0 degrees 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 And the diffraction peaks at about 43.0 degrees and about 45.0 degrees are obviously strengthened and shifted to the left, and due to the fact that the catalyst S-2 with the regular structure is treated by the carbon-containing atmosphere, the diffraction peaks appear at 42.6 degrees and 44.9 degrees of 2 theta, and the diffraction peaks at 42.6 degrees and 44.9 degrees of 2 theta are FeC (Fe) 3 C and Fe 7 C 3 ) The diffraction peak of (1). In addition, the regular structure catalyst S-2 showed a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ 2. Theta. Was a diffraction peak of elemental cobalt, as compared with the regular structure catalyst S-4.
Example 3
(1) Adding 209g of pseudo-boehmite into 1.13kg of deionized water, pulping and dispersing, then adding 19.0mL of hydrochloric acid, acidifying for 15min to obtain an aluminum-aluminum colloid, and adding ferric nitrate (calculated as Fe) calculated as metal oxide 2 O 3 Calculated as Co) 20g, cobalt nitrate (calculated as Co) 2 O 3 Meter) 12g, KMnO 4 Adding 10g (calculated by MnO) into 350mL of water, stirring until the mixture is fully dissolved, adding the aluminum colloid into the mixture, and stirring for 15min to obtain a first solution; adding 24g of MgO into 72g of water, stirring for 10min, adding into the first solution, and stirring for 20min to obtain active component coating slurry;
(2) Coating cordierite honeycomb carrier (the carrier pore density is 400 pores per square inch, and the section is coated with the active component coating slurry obtained in the step (1)Has an open pore content of 70% and the shape of the pores is square), dried (100 ℃,4 hours), and then transferred to a tube furnace, where CO/N having a CO concentration of 10 vol% is introduced at a flow rate of 100mL/min 2 And treating the mixed gas at 650 ℃ for 1h to obtain an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier to obtain the regular structure catalyst S-3, wherein the content of the active component coating is 20 wt% based on the total weight of the regular structure catalyst.
The measurement results of the contents of the components in the active component coating of the catalyst S-3 with the regular structure are shown in Table 1.
The XRD analysis result of the regular structure catalyst S-3 was similar to that of example 1. In XRD spectrogram of regular structure catalyst S-3 treated in carbon-containing atmosphere, there are not only MgO diffraction peak at about 43.0 degrees, but also Al at about 45.0 degrees 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 And the diffraction peaks at about 43.0 degrees and about 45.0 degrees are obviously strengthened and shifted leftwards, and are attributed to that the diffraction peaks appear at 42.6 degrees and 44.9 degrees of 2 theta of the regular structure catalyst S-3 treated by the carbon-containing atmosphere, and the diffraction peaks at 42.6 degrees and 44.9 degrees of 2 theta are FeC (Fe) 3 C and Fe 7 C 3 ) The diffraction peak of (4). In addition, the regular structure catalyst S-3 showed a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ 2. Theta. Was a diffraction peak of elemental cobalt, as compared with the regular structure catalyst S-4.
Example 4
The procedure of example 1 was followed except that CO/N was adjusted to a CO concentration of 10 vol% 2 And replacing the mixed gas with air to obtain the catalyst S-4 with a regular structure.
The results of measuring the contents of the respective components in the regular structure catalyst S-4 are shown in Table 1. XRD analysis is carried out on the regular structure catalyst S-4, and from an XRD spectrogram (shown in figure 1), no obvious diffraction peaks exist at positions with 2 theta of 42.6 degrees, 44.2 degrees and 44.9 degrees, which proves that both Fe and Co in the regular structure catalyst S-4 exist in an oxide form.
Example 5
A structured catalyst S-5 was obtained by following the procedure of example 1, except that MgO was replaced with the same mass of CaO in terms of metal oxide.
The results of measuring the contents of the respective components in the regular structure catalyst S-5 are shown in Table 1. XRD analysis of the regular structure catalyst S-5 was similar to that of example 1. In XRD spectrogram of regular structure catalyst S-5 treated by carbon-containing atmosphere, diffraction peaks appear at 42.6 degrees and 44.9 degrees of 2 theta, and diffraction peaks at 42.6 degrees and 44.9 degrees of 2 theta are FeC (Fe) 3 C and Fe 7 C 3 ) The diffraction peak of (1). In addition, the regular structure catalyst S-5 showed a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ 2. Theta. Was a diffraction peak of elemental cobalt, as compared with the regular structure catalyst S-4.
Example 6
The procedure is as in example 1, except that, calculated as metal oxide, the same mass of CeCl is used 2 Replacement of KMnO 4 To obtain the catalyst S-6 with a regular structure.
The results of measuring the contents of the respective components in the regular structure catalyst S-6 are shown in Table 1. XRD analysis of the regular structure catalyst S-6 was similar to that of example 1. In XRD spectrogram of regular structure catalyst S-6 treated by carbon-containing atmosphere, there are not only MgO diffraction peak around 43.0 degrees, but also Al around 45.0 degrees 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 And the diffraction peaks at about 43.0 degrees and about 45.0 degrees are obviously strengthened and shifted to the left, and due to the fact that the catalyst S-6 with the regular structure is treated by the carbon-containing atmosphere, the diffraction peaks appear at 42.6 degrees and 44.9 degrees of 2 theta, and the diffraction peaks at 42.6 degrees and 44.9 degrees of 2 theta are FeC (Fe) 3 C and Fe 7 C 3 ) The diffraction peak of (1). In addition, the regular structure catalyst S-6 showed a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ 2. Theta. Was a diffraction peak of elemental cobalt, as compared with the regular structure catalyst S-4.
Example 7
A regular structure catalyst S-7 was obtained in the same manner as in example 1 except that the amount of iron nitrate was 3g and the amount of cobalt nitrate was 9g, based on the metal oxide.
The results of measuring the contents of the respective components in the regular structure catalyst S-7 are shown in Table 1. XRD decomposition of regular structure catalyst S-7The results were similar to example 1. In XRD spectrogram of regular structure catalyst S-7 treated in carbon-containing atmosphere, there are not only MgO diffraction peak at about 43.0 degrees, but also Al at about 45.0 degrees 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 And the diffraction peaks at about 43.0 degrees and about 45.0 degrees are obviously strengthened and shifted leftwards, and are attributed to that the diffraction peaks appear at 42.6 degrees and 44.9 degrees of 2 theta of the regular structure catalyst S-7 treated by the carbon-containing atmosphere, and the diffraction peaks at 42.6 degrees and 44.9 degrees of 2 theta are FeC (Fe) 3 C and Fe 7 C 3 ) The diffraction peak of (1). In addition, compared with the regular structure catalyst S-4, the regular structure catalyst S-7 has a diffraction peak at 44.2 degrees, and the diffraction peak at 44.2 degrees 2 theta is the diffraction peak of simple substance cobalt.
Example 8
A regular structure catalyst S-8 was obtained in the same manner as in example 1 except that 9g of iron nitrate and 3g of cobalt nitrate were used in terms of metal oxide.
The results of measuring the contents of the respective components in the regular structure catalyst S-8 are shown in Table 1. XRD analysis of the regular structure catalyst S-8 was similar to that of example 1. In XRD spectrogram of regular structure catalyst S-8 treated in carbon-containing atmosphere, there are not only MgO diffraction peak at about 43.0 degrees, but also Al at about 45.0 degrees 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 And the diffraction peaks at about 43.0 degrees and about 45.0 degrees are obviously strengthened and shifted to the left, and due to the fact that the catalyst S-8 with the regular structure is treated by the carbon-containing atmosphere, the diffraction peaks appear at 42.6 degrees and 44.9 degrees of 2 theta, and the diffraction peaks at 42.6 degrees and 44.9 degrees of 2 theta are FeC (Fe) 3 C and Fe 7 C 3 ) The diffraction peak of (1). In addition, compared with the regular structure catalyst S-4, the regular structure catalyst S-8 has a diffraction peak at 44.2 degrees, and the diffraction peak at 44.2 degrees 2 theta is the diffraction peak of simple substance cobalt.
Example 9
The procedure of example 1 was followed except that the CO/N concentration of 10 vol% was replaced with an ethane/nitrogen mixed gas having an ethane concentration of 10 vol% 2 Mixing the gases to obtainRegular structure catalyst S-9.
The results of measuring the contents of the respective components in the regular structure catalyst S-9 are shown in Table 1. XRD analysis of the regular structure catalyst S-9 was similar to that of example 1. In XRD spectrogram of regular structure catalyst S-9 treated in carbon-containing atmosphere, there are not only MgO diffraction peak at about 43.0 degrees, but also Al at about 45.0 degrees 2 O 3 、Co 2 AlO 4 And MgAl 2 O 4 And the diffraction peaks at about 43.0 degrees and about 45.0 degrees are obviously strengthened and shifted to the left, and due to the fact that the catalyst S-9 with the regular structure is treated by the carbon-containing atmosphere, the diffraction peaks appear at 42.6 degrees and 44.9 degrees of 2 theta, and the diffraction peaks at 42.6 degrees and 44.9 degrees of 2 theta are FeC (Fe) 3 C and Fe 7 C 3 ) The diffraction peak of (1). In addition, the regular structure catalyst S-9 showed a diffraction peak at 44.2 ℃ and a diffraction peak at 44.2 ℃ 2. Theta. Was a diffraction peak of elemental cobalt, as compared with the regular structure catalyst S-4.
Comparative example 1
A regular structure catalyst D-1 was obtained by following the procedure of example 1 except that the cobalt nitrate was replaced with the same mass of iron nitrate based on the metal oxide.
The results of measuring the contents of the respective components in the regular structure catalyst D-1 are shown in Table 1.
Comparative example 2
A regular structure catalyst D-2 was obtained by following the procedure of example 1 except that the iron nitrate was replaced with the same mass of cobalt nitrate based on the metal oxide.
The results of measuring the contents of the respective components in the structured catalyst D-2 are shown in Table 1.
Comparative example 3
The catalyst precursor was prepared according to the method described in US6800586 and the structured catalyst was prepared according to the method in CN 1199733C. Specifically, 34.4 g of dried gamma-alumina microsphere carrier is taken, alumina microspheres are impregnated by a solution prepared from 10.09g of cerium nitrate, 2.13g of lanthanum nitrate, 2.7g of copper nitrate and 18mL of water, and after impregnation, the catalyst precursor is obtained after drying at 120 ℃ and roasting at 600 ℃ for 1 hour. 10g of catalyst precursor and 30g of alumina sol (with a solid content of 21.5%) are mixed and then coated on a cordierite-coated honeycomb carrier (with a carrier pore density of 400 pores per square inch, an open pore rate of a cross section of 70% and a square pore shape), and the mixture is dried (100 ℃,4 hours) and calcined (400 ℃,2 hours) to obtain a regular structure catalyst D-3, wherein the content of an active component coating is 25 wt% based on the total weight of the regular structure catalyst.
TABLE 1
Note: the contents of the first metal element, the second metal element and the third metal element are calculated by oxide, and the unit is weight percent.
Test example 1
The experimental example is used for reducing the NOx emission in the incomplete regeneration smoke under the aerobic condition of the catalysts provided by the example and the comparative example. Specifically, the regular structure catalyst is aged for 12 hours at 800 ℃ in the 100% water vapor atmosphere, and then the evaluation of the incompletely regenerated flue gas by simulated catalytic cracking is carried out.
The evaluation of the incompletely regenerated flue gas is carried out on a fixed bed simulated flue gas NOx reduction device, the catalyst with a regular structure is filled in a catalyst bed layer, the filling amount of the catalyst with the regular structure is 10g, the reaction temperature is 700 ℃, and the volume flow of the raw material gas is 1500mL/min (under the standard condition). The feed gas contained 3.7 vol.% CO,0.5 vol.% oxygen, 800ppm NH 3 The remainder being N 2 . Analyzing the gaseous product by an on-line infrared analyzer to obtain reacted NH 3 NOx and CO concentrations, and the results are shown in table 2.
TABLE 2
As can be seen from the data in Table 2, under the aerobic condition, the catalyst with the regular structure provided by the invention is used for the incomplete regeneration process of the catalytic cracking process, and has better NH reduction compared with the catalyst provided by the comparative example 3 And NOx emission performance, and an aged regular structure catalyst is used in the evaluation process, and NH is removed by the aged regular structure catalyst 3 And the NOx activity is still higher, so that the regular structure catalyst provided by the invention has better hydrothermal stability.
In the invention, test example 1 is adopted to simulate the effect of contact between the incompletely regenerated flue gas and the regular structure catalyst in the CO incinerator in the treatment process of the incompletely regenerated flue gas, and because air supplement exists in the CO incinerator and oxygen exists in the contact process, the flue gas provided by test example 1 of the invention has a certain amount of oxygen, and the effect of test example 1 of the invention can show that when the regular structure catalyst provided by the invention is used for being contacted with the incompletely regenerated flue gas in the CO incinerator, the regular structure catalyst provided by the invention has better NH (NH) resistance than the prior art 3 Catalytic conversion activity of reduced nitrides.
Test example 2
The experimental example is used for reducing the effect of NOx emission in incomplete regeneration smoke under the condition of oxygen deficiency on the catalysts provided by the example and the comparative example. Specifically, the regular structure catalyst is aged for 12 hours at 800 ℃ in the 100% water vapor atmosphere, and then the evaluation of incomplete regeneration flue gas by simulated catalytic cracking is carried out.
The evaluation of the incompletely regenerated flue gas is carried out on a fixed bed simulated flue gas NOx reduction device, a catalyst with a regular structure is filled in a catalyst bed layer, the filling amount of the catalyst with the regular structure is 10g, the reaction temperature is 650 ℃, and the volume flow of raw material gas is 1500mL/min (under a standard condition). The feed gas contained 3.7 vol.% CO,800ppm NH 3 The remainder being N 2 . Analyzing the gas product by an on-line infrared analyzer to obtain reacted NH 3 NOx and CO concentrations, and the results are shown in table 3.
TABLE 3
| Number of | NOx concentration, ppm | NH 3 Concentration in ppm | CO concentration,% by volume | |
| Example 1 | S-1 | 0 | 164 | 3.7 |
| Comparative example 1 | D-1 | 0 | 380 | 3.7 |
| Comparative example 2 | D-2 | 0 | 365 | 3.7 |
| Comparative example 3 | D-3 | 0 | 523 | 3.7 |
| Example 2 | S-2 | 0 | 141 | 3.7 |
| Example 3 | S-3 | 0 | 88 | 3.7 |
| Example 4 | S-4 | 0 | 190 | 3.7 |
| Example 5 | S-5 | 0 | 195 | 3.7 |
| Example 6 | S-6 | 0 | 200 | 3.7 |
| Example 7 | S-7 | 0 | 174 | 3.7 |
| Example 8 | S-8 | 0 | 171 | 3.7 |
| Example 9 | S-9 | 0 | 166 | 3.7 |
As can be seen from the data in Table 3, the use of the structured catalyst provided by the invention in the incomplete regeneration process of the catalytic cracking process under the oxygen-free condition has better NH reduction than the catalyst provided by the comparative example 3 The emission performance is evaluated by using an aged regular structure catalyst, and NH is removed from the aged regular structure catalyst 3 The activity is still higher, so the regular structure catalyst provided by the invention has better hydrothermal stability.
In the invention, test example 2 is adopted to simulate the effect of contact between the incompletely regenerated flue gas and the catalyst with the regular structure in the flue gas channel arranged in front of the CO incinerator in the treatment process of the incompletely regenerated flue gas, because the flue gas channel arranged in front of the CO incinerator is in an oxygen-poor state, and oxygen hardly exists in the contact process, the flue gas provided by the test example 2 does not contain oxygen, and the effect of the test example 2 can be shown that when the catalyst with the regular structure provided by the invention is used for contacting the incompletely regenerated flue gas in the flue gas channel arranged in front of the CO incinerator, the catalyst with the regular structure provided by the invention has better NH effect than the prior art 3 Catalytic conversion activity of reduced nitrides.
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.
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 (51)
1. A structured catalyst for reducing NOx emissions in flue gases, the catalyst comprising: the catalyst comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier, wherein the content of the active component coating is 10-50 wt% based on the total weight of the catalyst; the active component coating contains an active metal component and a substrate, the active metal component comprises a first metal element, a second metal element and a third metal element, the first metal element is selected from a VIII group non-noble metal element, the first metal element comprises Fe and Co, and the weight ratio of Fe to Co is 1: (0.05-20), the second metal element is selected from at least one of group IA and/or IIA metal elements, and the third metal element is selected from at least one of group IB-VIIB non-noble metal elements.
2. A structured catalyst according to claim 1, wherein the active component coating is present in an amount of 15 to 40 wt. -%, based on the total weight of the catalyst.
3. A structured catalyst according to claim 2, wherein the active component coating is present in an amount of 20 to 35 wt. -%, based on the total weight of the catalyst.
4. The structured catalyst of claim 1, wherein,
based on the total weight of the active component coating, the content of the substrate is 10-90 wt%, and calculated by oxide, the content of the first metal element is 0.5-50 wt%, the content of the second metal element is 0.5-20 wt%, and the content of the third metal element is 0.5-20 wt%.
5. The structured catalyst of claim 4, wherein,
based on the total weight of the active component coating, the content of the matrix is 50-90 wt%, and calculated by oxide, the content of the first metal element is 3-30 wt%, the content of the second metal element is 1-20 wt%, and the content of the third metal element is 1-10 wt%.
6. The structured catalyst of claim 5, wherein,
based on the total weight of the active component coating, the content of the substrate is 55-85 wt%, and calculated by oxide, the content of the first metal element is 5-25 wt%, the content of the second metal element is 5-15 wt%, and the content of the third metal element is 2-8 wt%.
7. A structured catalyst according to any one of claims 1 to 6, wherein the weight ratio Fe to Co, calculated as oxides, is 1: (0.1-10).
8. A structured catalyst according to claim 7, wherein the weight ratio of Fe to Co, calculated as oxides, is 1: (0.3-3).
9. A structured catalyst according to claim 8, wherein the weight ratio Fe to Co, calculated as oxides, is 1: (0.5-2).
10. A structured catalyst according to any of claims 1-6, 8-9, wherein Fe in the catalyst is at least partly present in the form of iron carbide; the Co in the catalyst is at least partially present as elemental cobalt.
11. A structured catalyst according to any one of claims 1 to 6, 8 to 9 wherein the catalyst has an XRD pattern with diffraction peaks at 42.6 °, 44.2 ° and 44.9 ° 2 Θ.
12. The structured catalyst according to any one of claims 1 to 6, 8 to 9, wherein the second metal element is selected from at least one of Na, K, mg and Ca;
the third metal element is at least one selected from Cu, zn, ti, zr, V, cr, mo, W, mn and rare earth elements.
13. The structured catalyst according to claim 12, wherein the second metal element is K and/or Mg;
the third metal element is at least one selected from Zr, V, W, mn, ce and La.
14. The structured catalyst of claim 13 wherein the second metal element is Mg;
the third metal element is Mn.
15. A structured catalyst according to any one of claims 1 to 6, 8 to 9, 13 to 14, wherein the matrix is selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite and perovskite.
16. A structured catalyst according to claim 15 wherein the matrix is selected from at least one of alumina, spinel and perovskite.
17. A structured catalyst according to claim 16 wherein the matrix is alumina.
18. A structured catalyst according to any one of claims 1 to 6, 8 to 9, 13 to 14, 16 to 17, wherein the structured support is selected from monolithic supports having a parallel cell structure with open ends.
19. A structured catalyst according to claim 18 wherein the cross-section of the structured carrier has a pore density of 20 to 900 pores per square inch and an open porosity of 20 to 80%.
20. A structured catalyst according to any one of claims 1 to 6, 8 to 9, 13 to 14, 16 to 17, and 19, wherein the structured carrier is selected from at least one of a cordierite honeycomb carrier, a mullite honeycomb carrier, a diamond honeycomb carrier, a corundum honeycomb carrier, a zirconia corundum honeycomb carrier, a quartz honeycomb carrier, a nepheline honeycomb carrier, a feldspar honeycomb carrier, an alumina honeycomb carrier, and a metal alloy honeycomb carrier.
21. A method of preparing a structured catalyst for reducing NOx emissions in flue gases, the method comprising:
(1) Mixing and pulping a substrate source, a first metal element precursor, a second metal element precursor, a third metal element precursor and water to obtain active component coating slurry;
(2) Coating a regular structure carrier with the active component coating slurry, and drying and roasting to obtain an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier;
the first metal element is selected from VIII group non-noble metal elements, the first metal element comprises Fe and Co, the second metal element is selected from at least one of IA group metal elements and/or IIA group metal elements, and the third metal element is selected from at least one of IB-VIIB group non-noble metal elements;
in the first metal element precursor, the use amounts of the precursor of Fe and the precursor of Co are such that, in the prepared catalyst, the weight ratio of Fe to Co is 1: (0.05-20).
22. The method of claim 21, wherein the firing conditions comprise: under the carbon-containing atmosphere, the temperature is 400-1000 ℃, and the time is 0.1-10h.
23. The method of claim 22, wherein the firing conditions include: under the carbon-containing atmosphere, the temperature is 450-650 ℃, and the time is 1-3h.
24. The method of claim 22 or 23, wherein the carbon-containing atmosphere is provided by a carbon-element-containing gas selected from at least one of CO, methane and ethane.
25. The method of claim 24, wherein the elemental carbon-containing gas is CO.
26. The method of claim 25, wherein the carbon-containing atmosphere has a concentration of CO in the range of 1-20% by volume.
27. The method of claim 26, wherein the volume concentration of CO in the carbon-containing atmosphere is 4-10%.
28. The method of any of claims 21-23, 25-27, wherein the coating is such that the active ingredient coating is present in an amount of 10-50 wt% based on the total amount of catalyst in the resulting catalyst.
29. The method as claimed in claim 28, wherein the coating is such that the active component coating is contained in the prepared catalyst in an amount of 15 to 40 wt% based on the total amount of the catalyst.
30. The method of claim 29, wherein the coating is such that the active component coating is present in the catalyst in an amount of 20 to 35 wt.%, based on the total amount of catalyst.
31. The method of any of claims 21-23 and 25-27, wherein the substrate source, the first metal element precursor, the second metal element precursor, and the third metal element precursor are used in an amount to produce a catalyst having a substrate content of 10 to 90 wt%, a first metal element content of 0.5 to 50 wt%, a second metal element content of 0.5 to 20 wt%, and a third metal element content of 0.5 to 20 wt%, as oxides, based on the total weight of the active component coating.
32. The method according to claim 31, wherein the matrix source, the first metal element precursor, the second metal element precursor and the third metal element precursor are used in amounts such that the matrix is contained in an amount of 50 to 90 wt%, the first metal element is contained in an amount of 3 to 30 wt%, the second metal element is contained in an amount of 1 to 20 wt% and the third metal element is contained in an amount of 1 to 10 wt%, in terms of oxide, based on the total weight of the active component coating layer in the resultant catalyst.
33. The method of claim 32, wherein the substrate source, first metal element precursor, second metal element precursor, and third metal element precursor are used in amounts such that the resulting catalyst has a substrate content of 55 to 85 wt%, a first metal element content of 5 to 25 wt%, a second metal element content of 5 to 15 wt%, and a third metal element content of 2 to 8 wt%, calculated as oxide, based on the total weight of the active component coating.
34. The method of any of claims 21-23, 25-27, 29-30, 32-33, wherein the Fe and Co precursors are used in amounts such that the resulting catalyst has a weight ratio of Fe to Co, calculated as oxides, of 1: (0.1-10).
35. The method as claimed in claim 34, wherein the Fe and Co precursors are used in amounts such that the weight ratio of Fe to Co, calculated as oxides, in the resulting catalyst is 1 (0.3-3).
36. The method of claim 35, wherein the Fe and Co precursors are used in amounts such that the resulting catalyst has a weight ratio of Fe to Co, calculated as oxides, of 1: (0.5-2).
37. The method of any one of claims 21-23, 25-27, 29-30, 32-33, 35-36, wherein the second metallic element is selected from at least one of Na, K, mg, and Ca;
the third metal element is at least one of Cu, zn, ti, zr, V, cr, mo, W, mn and rare earth elements;
the first metal element precursor, the second metal element precursor and the third metal element precursor are respectively selected from water-soluble salts of the first metal element, the second metal element and the third metal element.
38. The method of claim 37, wherein the second metallic element is K and/or Mg;
the third metal element is at least one selected from Zr, V, W, mn, ce and La.
39. The method of claim 38, wherein the second metallic element is Mg;
the third metal element is Mn.
40. The method of any of claims 21-23, 25-27, 29-30, 32-33, 35-36, 38-39, wherein the substrate source is a substance that is convertible to a substrate under the conditions of the firing of step (2);
the matrix is selected from at least one of alumina, silica-alumina, zeolite, spinel, kaolin, diatomaceous earth, perlite and perovskite.
41. The method of claim 40, wherein the matrix is selected from at least one of alumina, spinel, and perovskite.
42. The method of claim 41, wherein the substrate is alumina.
43. The method of any of claims 21-23, 25-27, 29-30, 32-33, 35-36, 38-39, wherein the structured support is selected from monolithic supports having a parallel cell structure with open ends.
44. The method as in claim 43, the structured carrier having a cross-section with a cell density of 20 to 900 cells per square inch and an open cell content of 20 to 80 percent.
45. The method of any of claims 21-23, 25-27, 29-30, 32-33, 35-36, 38-39, wherein the structured carrier is selected from at least one of a cordierite honeycomb carrier, a mullite honeycomb carrier, a diamond honeycomb carrier, a corundum honeycomb carrier, a zircon corundum honeycomb carrier, a quartz honeycomb carrier, a nepheline honeycomb carrier, a feldspar honeycomb carrier, an alumina honeycomb carrier, and a metal alloy honeycomb carrier.
46. A structured catalyst for reducing NOx emissions from flue gases produced by the method of any one of claims 21 to 45.
47. Use of a structured catalyst as claimed in any one of claims 1 to 20 and 46 for reducing NOx emissions from flue gases in catalytic cracking of incompletely regenerated flue gases.
48. A method for treating incomplete regeneration flue gas, the method comprising: contacting incomplete regeneration flue gas with a catalyst, wherein the catalyst is the structured catalyst for reducing NOx emission in incomplete regeneration flue gas as described in any one of claims 1 to 20 and 46.
49. A treatment process according to claim 48, wherein the contacting is carried out in a flue gas channel provided in front of and/or in front of a CO incinerator.
50. The process of claim 49, wherein the contacting is carried out in a flue gas channel provided in front of a CO incinerator.
51. The process of claim 48, wherein the conditions of the contacting comprise: the temperature is 600-1000 ℃, the reaction pressure is 0-0.5MPa, and the mass space velocity of the flue gas is 10-1000h -1 。
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| CN106955703A (en) * | 2017-03-13 | 2017-07-18 | 中国石油大学(北京) | The co-catalyst of pollutant emission and its application in a kind of reduction regenerated flue gas |
| CN108404951A (en) * | 2017-02-10 | 2018-08-17 | 中国石油化工股份有限公司 | The method of ordered structure desulphurization catalyst and preparation method thereof and sulfur-bearing hydrocarbon desulfurization |
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| CN108404951A (en) * | 2017-02-10 | 2018-08-17 | 中国石油化工股份有限公司 | The method of ordered structure desulphurization catalyst and preparation method thereof and sulfur-bearing hydrocarbon desulfurization |
| CN106955703A (en) * | 2017-03-13 | 2017-07-18 | 中国石油大学(北京) | The co-catalyst of pollutant emission and its application in a kind of reduction regenerated flue gas |
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