CN108295859B - Preparation method and application of Ni-based catalyst microspheres - Google Patents
Preparation method and application of Ni-based catalyst microspheres Download PDFInfo
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- CN108295859B CN108295859B CN201810089987.7A CN201810089987A CN108295859B CN 108295859 B CN108295859 B CN 108295859B CN 201810089987 A CN201810089987 A CN 201810089987A CN 108295859 B CN108295859 B CN 108295859B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 239000004005 microsphere Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000007921 spray Substances 0.000 claims abstract description 18
- 238000005470 impregnation Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000003245 coal Substances 0.000 claims abstract description 7
- 238000002309 gasification Methods 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 45
- 239000003921 oil Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000005299 abrasion Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 12
- 238000005507 spraying Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000007599 discharging Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910002339 La(NO3)3 Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002549 Fe–Cu Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J35/51—Spheres
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- C07C2529/14—Iron group metals or copper
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention provides a preparation method and application of Ni-based catalyst microspheres. The preparation method of the Ni-based catalyst microsphere comprises the following steps: 1) preparing a Ni-based catalyst microsphere carrier: modifying the carrier microsphere to obtain a modified carrier microsphere as a carrier of the Ni-based catalyst microsphere; 2) depositing active components on the surface of the modified carrier microspheres obtained in the step 1) by adopting a spray impregnation method; 3) drying and roasting the microspheres obtained in the step 2) to obtain the Ni-based catalyst microspheres. The Ni-based catalyst microspheres prepared by the preparation method of the Ni-based catalyst microspheres have good wear resistance, the wear index can be reduced to below 1.5, and the catalytic activity is high when the Ni-based catalyst microspheres are used in the fluidized bed methanation process of synthesis gas obtained by coal gasification. The preparation method of the Ni-based catalyst microsphere has the advantages of simple and easily-controlled preparation process and large treatment capacity, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis, and relates to a preparation method and application of Ni-based catalyst microspheres.
Background
The high-efficiency heat and mass transfer performance makes the fluidized bed especially suitable for various strong heat release technological processes. The bubbling fluidized bed is used as a catalytic reactor, the reaction is basically carried out under an isothermal condition except for high-efficiency heat and mass transfer efficiency, heat transfer can be easily realized by adjusting the flow and temperature of a heat exchange medium entering a built-in heat exchange coil, so that the service life of the catalyst is prolonged, and meanwhile, the catalyst is convenient to update because particles are in a flowing state.
In the prior art, the methanation process of the synthesis gas is a rapid and strong heat release process, the adiabatic temperature rise of a bed layer is rapid, the product purity is easily reduced due to the increase of the operation temperature, and the catalyst is inactivated. Currently, the commercial methanation technology uses adiabatic multistage fixed bed technology with a tableted (porous) cylindrical catalyst. However, the adiabatic multistage fixed bed methanation process only depends on gas flow to transfer methanation reaction heat, and because the gas heat capacity is small, the process can reduce the bed temperature of the catalyst only by adopting technical methods such as multistage reaction, raw gas diversion, product gas circulation and the like, so that the process has weak anti-interference capability and needs to improve the energy efficiency; at the same time, the service life and the start-up time of the catalyst can be ensured only by using excessive catalyst. In 1963, the Bi-Gas process developed by BCR company in America adopts a fluidized bed as a methanation reactor, 2 heat exchange tubes are arranged in the fluidized bed, reaction heat is removed by mineral oil in the tubes, and the CO conversion rate can be improved to 96-99.2% by improving a catalyst.
Although the fluidized bed methanation reactor has good reaction effect and high methane yield, the entrainment and loss of the catalyst are serious. The results of the study show that the attrition loss of the catalyst for fluidized bed methanation depends mainly on the attrition resistance of the catalyst, but its effect decreases with time on stream and may eventually stabilize. At present, in the aspect of improving the wear resistance of the fluidized bed catalyst, the methods generally adopted by researchers mainly focus on the following two aspects:
(1) spray granulation method for catalyst forming
CN103706393A discloses a preparation method of an abrasion-resistant catalyst microsphere for producing low-carbon olefin, which comprises the following steps: 1) dispersing a molecular sieve and a matrix in deionized water, homogenizing and stirring for 1-3 hours, adding a mother solution obtained by synthesizing the molecular sieve, and continuously stirring for 1-5 hours to obtain a mixture slurry; 2) grinding the mixture slurry obtained in the step 1) for 1-5 hours by using a rubber grinder, and spray-drying the mixture slurry obtained after grinding to obtain catalyst microspheres; 3) and (3) roasting the catalyst microspheres obtained in the step 2) to obtain the wear-resistant catalyst microspheres for the reaction of preparing olefin from methanol. CN101242900A discloses a method for preparing a catalyst for use in a process for converting oxygenates to olefins, comprising: providing a reaction mixture containing aluminum, phosphorus, water, an organic template, and an element selected from the group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium, and mixtures thereof, to form a non-zeolitic molecular sieve having a chemical composition on an anhydrous basis represented by the empirical formula: (ElxAlyPz)O2Wherein "x" is the mole fraction of El and has a value of at least 0.001 and "y" is the mole fraction of A1And having a value of at least 0.01, "z" is the mole fraction of P and has a value of at least 0.01 and x + y + z is 1, crystallizing the molecular sieve at a temperature between 100 ℃ and 250 ℃; and washing the molecular sieve; adding a first binder comprising sodium silicate and acid alum to the washed molecular sieve to form a catalyst slurry; the catalyst slurry is spray dried and calcined at a temperature above 500 ℃ to obtain the attrition resistant catalyst. CN1395992A discloses a preparation method of a microspherical Fischer-Tropsch synthesis catalyst, which comprises the following steps: 1) the catalyst comprises the following components in percentage by weight of Fe, La, Cu, K and SiO2Uniformly mixing ferric nitrate or ferric sulfate, lanthanum nitrate, cupric nitrate or copper sulfate solution to prepare solution with the total mole number of 1-5 mol/L, and then adding Na (sodium nitrite) to the solution, wherein the ratio of the ferric nitrate or ferric sulfate to the solution is 0.01-5: 0.5-15: 0.5-10: 5-302CO3Or ammonia water forms precipitation slurry, and the precipitation slurry is washed and filtered to obtain a coprecipitation filter cake; 2) adding SiO into the coprecipitation filter cake according to the composition of the catalyst2:K2O modulus of 1 to 10, SiO2Uniformly mixing 5-30 wt% of potassium silicate water glass solution, adding deionized water, and pulping to obtain catalyst slurry with the solid content of 10-40 wt%; 3) feeding the catalyst slurry into a centrifugal spray dryer, and carrying out spray drying under the conditions that the inlet temperature of hot air is 200-350 ℃ and the outlet temperature of exhaust air is 100-180 ℃; 4) roasting the powder after spray drying at the roasting temperature of 300-450 ℃ for 2-12 hours to obtain microspherical slurry bed Fischer-Tropsch synthesis Fe/La/Cu/K/SiO2A catalyst. The three patents respectively adopt spray granulation to prepare catalyst microspheres for producing low-carbon olefin by taking a molecular sieve as a precursor and producing MTO and Fe-Cu series Fischer-Tropsch synthesis by taking SAPO-34 as a precursor, and the abrasion indexes are respectively as low as 0.5(ASTM method), 0.1-0.2(Katalistiks method) and 1.0-2.2(ASTM method). CN105381803A discloses a fluidized bed catalyst for methanation of synthesis gas, which comprises: the catalyst comprises an active component Ni accounting for 5-75% of the total weight of the catalyst, an auxiliary agent M accounting for 0.1-50% of the total weight of the catalyst and a carrier Al2O3 accounting for the balance, wherein the auxiliary agent M is one or more oxides of Fe, Co, Mo, Si, Mg, Ca, Sc, Cr, Ti, Y, Zr, La, Ce, Yb and Sm. CN106925333A discloses synthesis gas methanationThe fluidized bed catalyst of (a), comprising: the catalyst comprises an active component Ni accounting for 2-65% of the total weight of the catalyst, an auxiliary agent M accounting for 0.1-50% of the total weight of the catalyst, a first carrier ZrO2 accounting for 1-80% of the total weight of the catalyst and the balance of a second carrier, wherein the auxiliary agent M is one or more oxides of Fe, Co, Mo, Mg, Sc, Cr, Ti, Al, Y, La, Ce, Yb and Sm, and the second carrier is one or more molecular sieves of ZSM-5, SAPO-34 and MCM-41. The preparation method of the two synthesis gas methanation fluidized bed catalysts comprises the steps of preparation of Ni-based catalyst slurry and spray granulation of the Ni-based catalyst slurry, but the abrasion strength of the catalyst is not analyzed.
(2) The active component of the catalyst is loaded on the high-strength carrier microsphere, thereby improving the wear resistance of the catalyst
We et Al (Applied Catalysis A: General 2001, 210:137-2O3And SiO2The strength of the loaded catalyst is better, and the influence of the loaded metal on the strength of the carrier is not large.
However, the research on the preparation method of the Ni-based catalyst microspheres is less, so that the development of a preparation method of the high-efficiency wear-resistant Ni-based catalyst microspheres is very meaningful.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of Ni-based catalyst microspheres, which have good wear resistance and high catalytic activity when being used in the fluidized bed methanation process of synthesis gas obtained by coal gasification.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of Ni-based catalyst microspheres comprises the following steps:
1) preparing a Ni-based catalyst microsphere carrier: modifying the carrier microsphere to obtain a modified carrier microsphere as a carrier of the Ni-based catalyst microsphere;
2) depositing active components on the surface of the modified carrier microspheres obtained in the step 1) by adopting a spray impregnation method;
3) drying and roasting the microspheres obtained in the step 2) to obtain the Ni-based catalyst microspheres.
In the present invention, the carrier microsphere FCC microsphere and/or Al of step 1)2O3Microspheres, either fresh/aged/spent FCC microspheres or Al2O3And (3) microspheres. The catalytic cracking (FCC) catalyst is the most applied catalyst in oil refining industry and mainly comprises kaolin and Al2O3And a small amount of Y-type or ZSM-5 molecular sieve, the abrasion index can be as low as 0.8-2.5, and the catalyst is a high abrasion-resistant catalyst successfully applied to a fluidized bed reactor at present. But it is deactivated and discarded by absorbing Ni, V and Fe ions in petroleum in the process of petroleum catalytic cracking, and the landfill method is generally adopted for treating FCC spent catalyst, thereby causing pollution of soil, water resource and atmosphere. Preferably, the carrier microspheres are prepared by spray granulation. Al (Al)2O3The microsphere can be prepared by directly using pseudo-boehmite as a raw material and carrying out spray granulation.
Fresh/aged/spent FCC microspheres cannot be used directly as a support for Ni-based catalysts due to their small pore size and need to be modified.
As a preferable scheme, in the step 1), the modifying method is to load an auxiliary agent on the carrier microsphere; namely, using Al (NO)3)3、Mg(NO3)2Modifying the microspheres with an acidic solution, and loading auxiliary agent active Al on the carrier microspheres2O3And/or active MgO, on one hand, the aperture and the specific surface area of the FCC catalyst microsphere can be improved, and on the other hand, the acidity and alkalinity of the surface of the catalyst can be improved, so that the catalyst is beneficial to the occurrence of methanation reaction to inhibit carbon deposition reaction.
As another preferred scheme, in step 1), the modification method is to bake the carrier microspheres at a high temperature. Al prepared by directly spraying and granulating pseudo-boehmite as raw material2O3The abrasion index of the microspheres is as high as 2.5-3, the abrasion resistance of the microspheres needs to be improved by high-temperature roasting, and preferably, in the step 1), the high-temperature roasting temperature is 800-1400 ℃.
In step 2), freshAged/spent FCC microspheres or Al2O3The component gamma-Al in the microsphere2O3The catalyst microsphere can be partially or completely converted into boehmite AlOOH in a water-containing atmosphere, and the change of a crystalline phase causes the surface area and the pore volume to be greatly reduced on one hand, the average pore diameter to be obviously reduced, and the mechanical strength to be greatly reduced on the other hand, so the invention adopts a spray impregnation method to reduce the contact time of an aqueous solution of an active component Ni or an auxiliary agent and a carrier as much as possible, and ensures the abrasion strength of the catalyst microsphere.
In order to ensure rapid diffusion and sufficient impregnation of the active component in a short time, in step 2), the active component is Ni; more preferably, in step 2), the active component further comprises an auxiliary agent, i.e. the active component is Ni and the auxiliary agent; further preferably, the pressure for depositing the active component in the spraying and dipping method is 0.06Pa to 101.325 KPa. In a vacuum environment, a large amount of gas in carrier channels escapes in the evacuation process, the reserved gaps and channels not only promote the infiltration of impregnation liquid, but also have small absolute values of the partial pressure of the residual gas in the gaps and the environmental pressure, a new equilibrium state is formed between a system and a low-pressure environment, the capability of hindering the migration and movement of substances is weakened, and the diffusion process is facilitated.
In the step 2), the auxiliary agent is one or a mixture of at least two of magnesium nitrate, lanthanum nitrate, zirconium nitrate and zirconium oxychloride. Typical but non-limiting combinations of the mixtures are mixtures of magnesium nitrate, lanthanum nitrate, mixtures of magnesium nitrate, zirconium oxychloride, mixtures of magnesium nitrate, lanthanum nitrate, zirconium nitrate, mixtures of magnesium nitrate, lanthanum nitrate, zirconium oxychloride, mixtures of lanthanum nitrate, zirconium nitrate and zirconium oxychloride, mixtures of magnesium nitrate, lanthanum nitrate, zirconium nitrate and zirconium oxychloride.
In the step 3), the drying temperature is 60-150 ℃; the drying time is 4-12 h.
Ni/Al2O3The roasting temperature of the catalyst directly influences the interaction between the active component and the carrier, and further influences the reduction temperature of the catalyst and the size of active metal Ni. In the step 3), the roasting temperature is 400-700 DEGDEG C; the roasting time is 2-6 h.
The second purpose of the present invention is to provide Ni-based catalyst microspheres.
The third purpose of the invention is to provide the application of the Ni-based catalyst microspheres, and the catalyst prepared by the preparation method of the Ni-based catalyst microspheres can be used for the fluidized bed high-temperature high-pressure methanation process of synthesis gas obtained by coal gasification; the catalyst has good catalytic activity and stability within the application range of 300-650 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the Ni-based catalyst microsphere prepared by the preparation method of the Ni-based catalyst microsphere has good wear resistance, the wear index can be reduced to below 1.5, the catalytic activity is high when the Ni-based catalyst microsphere is used in the fluidized bed methanation process of synthesis gas obtained by coal gasification, the Ni-based catalyst microsphere has good catalytic activity and stability within the use range of 300-650 ℃, and the conversion rate of CO is 24.8-38.4% at the reaction space velocity of 120000 mL/(g.h).
(2) The preparation method of the Ni-based catalyst microsphere has the advantages of simple and easily-controlled preparation process and large treatment capacity, and is suitable for industrial large-scale production.
Drawings
Fig. 1 is a schematic view of equipment used in a drying process for impregnation in the preparation method of Ni-based catalyst microspheres according to the present invention.
The reference numbers are as follows:
1-carrier microspheres; 2-a reaction kettle; 3-a spray pipe; 4-steam valve/thermal oil valve; 5-evacuation tube.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments with reference to fig. 1.
Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.
The impregnation and drying of the Ni-based catalyst microspheres of the present invention may be simultaneously accomplished in the apparatus shown in fig. 1. (1) And (3) dipping: putting the high-strength carrier microspheres 1 into a reaction kettle 2, sealing a feed inlet, starting a vacuum pump after air tightness, starting a rotary drum in a negative pressure state, enabling the carrier microspheres 1 to uniformly rotate in the reaction kettle 2, uniformly and rapidly spraying impregnation liquid through a spray pipe 3, and controlling liquid inlet time. And after the impregnation liquid is completely fed, maintaining the negative pressure state until the impregnation process is completed. (2) And (3) drying: opening the jacket steam valve/heat-conducting oil valve 4 of the reaction kettle 2, heating the reaction kettle 2 by steam or heat-conducting oil, controlling the vacuum degree of the reaction kettle 2 and the steam pressure or temperature of the jacket, starting vaporization of water in the reaction kettle 2, and pumping out the water from the reaction system through the vacuum pumping pipe 5 to achieve the effect of primary drying.
Example 1
Preparation of catalyst A
1) 3kg of fresh FCC were weighed into a continuously rotating reaction vessel as shown in FIG. 1, and 2.67kg of Al (NO) was added3)3·9H2Dissolving O with deionized water, continuously spraying the dissolved O into a reaction kettle, maintaining the temperature of a jacket of the reaction kettle to be 60 ℃ by adopting heat conducting oil in the reaction process, soaking for 6 hours in an equal volume, raising the temperature of the jacket of the reaction kettle to 150 ℃ by adopting the heat conducting oil, discharging the material after 2 hours, and roasting for 4 hours at 500 ℃ to obtain a modified FCC carrier;
2) the modified FCC carrier was again placed in a continuously rotating reaction vessel as shown in FIG. 1, and 3.97kg of Ni (NO) was added3)2·6H2O，0.67kg La(NO3)3·9H2O and 0.88kg Zr (NO)3)4·5H2Dissolving O in deionized water, continuously spraying the dissolved O into a reaction kettle, and maintaining the temperature of a jacket of the reaction kettle to be 60 ℃ by adopting heat conduction oil in the reaction process;
3) after soaking for 6h in the same volume, adopting heat conducting oil to raise the temperature of a reaction kettle jacket to 150 ℃, discharging the material after 2h, and roasting at 500 ℃ for 4h to obtain the catalyst A, wherein the main technical indexes are shown in the attached table 1.
Example 2
Preparation of catalyst B
1) 3kg of aged FCC was weighed into a continuously rotating reaction vessel as shown in FIG. 1, and 3.2kg of Mg (NO) was added3)2·6H2Dissolving O in deionized water, continuously spraying to a reaction kettle, and adoptingMaintaining the temperature of a reaction kettle jacket to be 60 ℃ by using heat conduction oil, performing isovolumetric impregnation for 6 hours, increasing the temperature of the reaction kettle jacket to 150 ℃ by using the heat conduction oil, discharging the material after 2 hours, and roasting at 500 ℃ for 4 hours to obtain a modified FCC carrier;
2) the modified FCC carrier was again placed in a continuously rotating reaction vessel as shown in FIG. 1, and 3.97kg of Ni (NO) was added3)2·6H2O，0.67kg La(NO3)3·9H2O and 0.88kg Zr (NO)3)4·5H2Dissolving O in deionized water, continuously spraying the dissolved O into a reaction kettle, and maintaining the temperature of a jacket of the reaction kettle to be 60 ℃ by adopting heat conduction oil in the reaction process;
3) after soaking for 6h in the same volume, adopting heat conducting oil to raise the temperature of a reaction kettle jacket to 150 ℃, discharging the material after 4h, and then roasting at 500 ℃ for 4h to obtain the catalyst B, wherein the main technical indexes are shown in the attached table 1.
Example 3
Preparation of catalyst C
1) 3kg of waste FCC was weighed into a continuously rotating reaction vessel as shown in FIG. 1, and 2.67kg of Al (NO) was added3)3·9H2O and 3.2kg Mg (NO)3)2·6H2Dissolving O with deionized water, continuously spraying the dissolved O into a reaction kettle, maintaining the temperature of a jacket of the reaction kettle to be 60 ℃ by adopting heat conducting oil in the reaction process, soaking for 6 hours in an equal volume, raising the temperature of the jacket of the reaction kettle to 150 ℃ by adopting the heat conducting oil, discharging the material after 2 hours, and roasting for 4 hours at 500 ℃ to obtain a modified FCC carrier;
2) the modified FCC carrier was again placed in a continuously rotating reaction vessel as shown in FIG. 1, and 3.97kg of Ni (NO) was added3)2·6H2O，0.67kg La(NO3)3·9H2O and 0.88kg Zr (NO)3)4·5H2Dissolving O in deionized water, continuously spraying the dissolved O into a reaction kettle, and maintaining the temperature of a jacket of the reaction kettle to be 60 ℃ by adopting heat conduction oil in the reaction process;
3) after soaking for 6h in the same volume, adopting heat conducting oil to raise the temperature of a reaction kettle jacket to 150 ℃, discharging the material after 12h, and roasting at 500 ℃ for 4h to obtain the catalyst C, wherein the main technical indexes are shown in the attached table 1.
Example 4
Preparation of catalyst D
1) Al obtained by spray granulation2O3Roasting the microspheres at 800 ℃ for 4 h;
2) 3kg of modified Al was weighed2O3The microspheres were placed in a continuously rotating reaction vessel as shown in FIG. 1, and 3.97kg of Ni (NO) was added3)2·6H2O，3.2kg Mg(NO3)2·6H2O，0.67kg La(NO3)3·9H2O and 0.88kg Zr (NO)3)4·5H2Dissolving O in deionized water, continuously spraying the dissolved O into a reaction kettle, and maintaining the temperature of a jacket of the reaction kettle to be 60 ℃ by adopting heat conduction oil in the reaction process;
3) after soaking for 6h in the same volume, adopting heat conducting oil to raise the temperature of a reaction kettle jacket to 150 ℃, discharging the material after 2h, and roasting at 500 ℃ for 4h to obtain the catalyst D, wherein the main technical indexes are shown in the attached table 1.
Example 5
Preparation of catalyst E
1) Al obtained by spray granulation2O3Roasting the microspheres at the high temperature of 1400 ℃ for 4 hours;
2) 3kg of modified Al was weighed2O3The microspheres were placed in a continuously rotating reaction vessel as shown in FIG. 1, and 3.97kg of Ni (NO) was added3)2·6H2O，3.2kg Mg(NO3)2·6H2O，0.67kg La(NO3)3·9H2O and 0.88kg Zr (NO)3)4·5H2Dissolving O in deionized water, continuously spraying the dissolved O into a reaction kettle, and maintaining the temperature of a jacket of the reaction kettle to be 60 ℃ by adopting heat conduction oil in the reaction process;
3) after soaking for 6h in the same volume, adopting heat conducting oil to raise the temperature of a reaction kettle jacket to 150 ℃, discharging the material after 2h, and then roasting at 400 ℃ for 6h to obtain the catalyst E, wherein the main technical indexes are shown in the attached table 1.
Example 6
Preparation of catalyst F
1) Al obtained by spray granulation2O3The microspheres are roasted at a high temperature of 1400 DEG C4h；
2) 3kg of modified Al was weighed2O3The microspheres were placed in a continuously rotating reaction vessel as shown in FIG. 1, and 3.97kg of Ni (NO) was added3)2·6H2O，3.2kg Mg(NO3)2·6H2O，0.67kg La(NO3)3·9H2O and 0.88kg Zr (NO)3)4·5H2Dissolving O in deionized water, continuously spraying the dissolved O into a reaction kettle, and maintaining the temperature of a jacket of the reaction kettle to be 60 ℃ by adopting heat conduction oil in the reaction process;
3) after soaking for 6h in the same volume, adopting heat conducting oil to raise the temperature of a reaction kettle jacket to 150 ℃, discharging the material after 2h, and roasting at 700 ℃ for 2h to obtain the catalyst F, wherein the main technical indexes are shown in the attached table 1.
The Ni-based catalyst microspheres prepared in examples 1-6 were used in a fluidized bed high temperature high pressure methanation process of syngas obtained by coal gasification. Wherein the specific reaction conditions are as follows: the reaction temperature is 500 ℃, the reaction temperature is normal pressure, and the reaction gas consists of H2:CO:N23:1:1, reaction space velocity: 120000 mL/(g.h). The experimental results of the performance of the Ni-based catalyst microspheres are shown in table 1.
The method for measuring the abrasion index of each Ni-based catalyst microsphere sample comprises the following steps: an air jet abrasion test system is built according to the method of ASTM D5757-00, the test sample amount is 35g, all catalyst particles are sieved before the test, particles with the particle size range of 40-125 mu m are sieved and subjected to an abrasion test, and particles with the particle size of less than 40 mu m in a fine powder collector and a particle abrasion tube after the 5h abrasion test are considered as fine powder generated by abrasion. The Attrition Index (AI) of a particle is defined as:
TABLE 1
| Examples of the invention | Abrasion Index (AI) | CO conversion (%) |
| Example 1 | 1.22 | 35.6 |
| Example 2 | 1.58 | 37.5 |
| Example 3 | 1.86 | 38.4 |
| Example 4 | 2.14 | 32.7 |
| Example 5 | 1.03 | 29.5 |
| Example 6 | 0.85 | 24.8 |
As can be seen from Table 1, the Ni-based catalyst microspheres prepared by the preparation method of the Ni-based catalyst microspheres have good wear resistance, the wear index is 0.8-2.2, the wear index can be reduced to below 1.5, the catalytic activity is high when the Ni-based catalyst microspheres are used in the fluidized bed methanation process of synthesis gas obtained by coal gasification, the catalyst activity and the stability are good within the use range of 300-650 ℃, and the conversion rate of CO is 24.8-38.4% at the reaction space velocity of 120000 mL/(g.h). The preparation method of the Ni-based catalyst microsphere has the advantages of simple and easily-controlled preparation process and large treatment capacity, and is suitable for industrial large-scale production.
The above examples are only intended to illustrate the detailed process of the present invention, and the present invention is not limited to the above detailed process, i.e., it is not intended that the present invention necessarily depends on the above detailed process for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (5)
1. A preparation method of Ni-based catalyst microspheres is characterized by comprising the following steps:
1) preparing a Ni-based catalyst microsphere carrier: modifying the carrier microsphere to obtain a modified carrier microsphere as a carrier of the Ni-based catalyst microsphere;
2) depositing an active component and an auxiliary agent on the surface of the modified carrier microsphere obtained in the step 1) by adopting a spray impregnation method, wherein the active component is Ni, and the auxiliary agent is one or a mixture of at least two of magnesium nitrate, lanthanum nitrate, zirconium nitrate and zirconium oxychloride;
3) drying and roasting the microspheres obtained in the step 2) to obtain the Ni-based catalyst microspheres;
in the step 1), the carrier microsphere is FCC microsphere and/or Al2O3Microspheres;
the carrier microsphere is prepared by spray granulation;
in the step 1), the modifying method comprises the steps of loading an auxiliary agent on the carrier microsphere and/or roasting the carrier microsphere at high temperature, wherein the auxiliary agent loaded on the carrier microsphere is active Al2O3And/or active MgO, wherein the high-temperature roasting temperature is 800-1400 ℃;
in the step 3), the roasting temperature is 400-700 ℃, and the roasting time is 2-6 h.
2. The method according to claim 1, wherein the pressure for depositing the active ingredient in the spray impregnation method is 0.06Pa to 101.325 KPa.
3. The preparation method according to claim 1, wherein in the step 3), the drying temperature is 60-150 ℃, and the drying time is 4-12 h.
4. Ni-based catalyst microspheres obtained by the production method according to any one of claims 1 to 3.
5. Use of Ni-based catalyst microspheres according to any one of claims 1 to 3 in a fluidized bed high temperature and high pressure methanation process of syngas obtained by coal gasification.
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| CN102600860A (en) * | 2012-02-15 | 2012-07-25 | 华东理工大学 | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof |
| CN105381803A (en) * | 2015-12-08 | 2016-03-09 | 大唐国际化工技术研究院有限公司 | Fluidized bed catalyst for syngas methanation, preparation method thereof and applications thereof |
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| CN105381803A (en) * | 2015-12-08 | 2016-03-09 | 大唐国际化工技术研究院有限公司 | Fluidized bed catalyst for syngas methanation, preparation method thereof and applications thereof |
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