CN111659251A - Low-cost hierarchical pore SAPO-34 molecular sieve and preparation method and application thereof - Google Patents
Low-cost hierarchical pore SAPO-34 molecular sieve and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 90
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011574 phosphorus Substances 0.000 claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N N,N-Diethylethanamine Substances CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 46
- 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
- 238000003756 stirring Methods 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000002699 waste material Substances 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000012876 carrier material Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- -1 consists of PO2+ Chemical compound 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a low-cost hierarchical pore SAPO-34 molecular sieve, and a preparation method and application thereof, and belongs to the technical field of molecular sieve synthesis. The invention provides a preparation method of an SAPO-34 molecular sieve by taking lithium silicon powder waste as a raw material, which comprises the following steps: washing, drying and sieving lithium silicon powder by acid to obtain powder; uniformly mixing water and a phosphorus source to obtain a phosphorus source liquid; mixing the powder and the phosphorus source liquid, adding a template agent, and uniformly mixing to obtain a mixed solution; aging the mixed solution at room temperature, and heating for hydrothermal crystallization to obtain a crystallized solution; and cooling, washing, filtering, drying and calcining the crystallized liquid to obtain the SAPO-34 molecular sieve. The method carries out resource utilization on the lithium silicon powder which is a large amount of piled up waste residues at present, simultaneously controls the using amount of each material and optimizes the synthesis conditions to ensure that the SAPO-34 molecular sieve has a micro-mesoporous and multi-stage pore structure, effectively overcomes the defect of a single microporous structure, and can be used as a carrier material of a low-temperature denitration catalyst.
Description
Technical Field
The invention belongs to the technical field of waste utilization and molecular sieve synthesis, and particularly relates to a low-cost hierarchical pore SAPO-34 molecular sieve, and a preparation method and application thereof.
Background
The SAPO-34 molecular sieve has a typical CHA topological structure, and the framework of the SAPO-34 molecular sieve mainly consists of PO2+、AlO2-、SiO2The tetrahedral body is connected with each other to form, and the framework atoms are periodically arranged and combined into a six-membered ring, a four-membered ring and an eight-membered ring to finally form an ellipsoidal CHA cage structure and a three-dimensional cross channel structure. SAPO-34 being essentially a Si atom substituted AlPO4Formed by framework atoms, since in AlPO4In the skeleton, PO2+And AlO2-The tetrahedra have positive and negative charges respectively, and the number of the tetrahedra is equivalent, so that the whole framework is electrically neutral externally, the surface acidity is weak, and NH is not facilitated3For NH in SCR reactions3Adsorption of (3). However, after the Si atoms are introduced into the framework, the original charge balance is destroyed, so that the whole molecular sieve is negatively charged. The surface of the SAPO-34 also has an L acid center and a B acid center. Therefore, SAPO-34 has been widely used in denitration catalysts due to its excellent hydrothermal stability, suitable surface acidity and pore structure.
At present, the synthesis methods of SAPO-34 mainly include four methods, namely a hydrothermal synthesis method, a gas phase crystallization method, a microwave synthesis method and an ultrasonic synthesis method. The hydrothermal synthesis method is the most widely and mature method at present, and the main raw materials comprise a silicon source, an aluminum source, a phosphorus source, a template agent and deionized water; commonly used silicon sources include silica sol, active SiO2And an orthosilicate; the aluminum source comprises activated alumina, pseudo-boehmite and aluminum isopropoxide; the template agent can adopt tetraethyl ammonium hydroxide (TEAOH), triethylamine, diethylamine, morpholine and the like; the phosphorus source is generally orthophosphoric acid.
CN106477595A mixes the double-template agent with a silicon source, an aluminum source and a phosphorus source, adopts a one-step hydrothermal crystallization method to prepare the SAPO-34 molecular sieve with the sheet shape, the grain size range of which is 0.5-2 um, and the SAPO-34 molecular sieve is used for preparing olefin by methanol. Dissolving soft template agent saccharides in water to prepare a template agent solution in CN110342539A, adding a silicon source, an aluminum source and a phosphorus source, and carrying out aging and hydrothermal crystallization to synthesize the hierarchical pore SAPO-34 molecular sieve. CN103145145A discloses a preparation method of SAPO-34 molecular sieve with A-type zeolite as silicon source, but the hydrothermal time is 3-6 days, and the A-type zeolite needs hydrothermal pretreatment.
In the preparation method of the SAPO-34 molecular sieve, chemical agents are completely adopted as raw materials, or the hydrothermal time is too long, or the synthesis process is complex, so that the cost is high, and the practical production application of the SAPO-34 molecular sieve is limited.
At present, the lithium silicon powder storage capacity is huge in China, however, only a small part of lithium silicon powder is used for concrete blending for secondary utilization, and most of the rest lithium silicon powder serving as industrial waste is generally disposed in an on-site open-air stacking or direct landfill mode. The lithium silicon powder is fine powder, and dust is easily generated in open-air stacking, so that the air environment is greatly damaged; direct landfill pollutes underground water resources; meanwhile, the open stacking is a waste of land resources. Therefore, it is required to develop a recycling process of lithium silicon powder waste.
Disclosure of Invention
Aiming at the problem of high cost of the existing preparation method, the invention provides a preparation method of a low-cost hierarchical pore SAPO-34 molecular sieve by using lithium silicon powder waste as a raw material, which comprises the following steps:
A. washing, drying and sieving lithium silicon powder by acid to obtain powder;
B. uniformly mixing water and a phosphorus source to obtain a phosphorus source liquid;
C. mixing the powder obtained in the step A and the phosphorus source liquid obtained in the step B, adding a template agent under a stirring state, and uniformly mixing to obtain a mixed liquid;
D. c, aging the mixed solution obtained in the step C at room temperature, and heating for hydrothermal crystallization to obtain a crystallized solution;
E. and D, cooling, washing, filtering, drying and calcining the crystallization liquid obtained in the step D to obtain the low-cost hierarchical pore SAPO-34 molecular sieve.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step A, the acid is at least one of hydrochloric acid, sulfuric acid and nitric acid.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step A, the concentration of the acid is 1-5 mol/L.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step A, active SiO in the lithium silicon powder2And Al2O3The total mass ratio of (A) is not less than 65%.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, the lithium silicon powder in the step A, the water in the step B, the phosphorus source in the step B and the template agent in the step C are added according to the adding amount of Al in the mixed liquid in the step C2O3、H3PO4、SiO2Triethylamine and H2The molar ratio of O is 1.0: 1.5-2.5: 0-1.5: 1-5: 30-100.
Preferably, in the preparation method of the low-cost multi-stage pore SAPO-34 molecular sieve, the lithium silicon powder in the step A, the water in the step B, the phosphorus source in the step B and the template in the step C are added according to the adding amount of Al in the mixed solution in the step C2O3、H3PO4、SiO2Triethylamine and H2The molar ratio of O is 1.0: 1.8-2.2: 0.6-1.0: 2.7-3.3: 40-60.
Wherein, in the preparation method of the low-cost hierarchical porous SAPO-34 molecular sieve, Al in lithium silicon powder is used as the Al2O3And when the aluminum source is insufficient, replenishing the aluminum source in the step B and uniformly mixing.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, the aluminum source is at least one of pseudo-boehmite, alumina, aluminum hydroxide, alumina sol or soluble aluminum salt.
Preferably, in the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, the aluminum source is alumina.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step B, the phosphorus source is at least one of phosphoric acid, ammonium phosphate, phosphite or soluble metal phosphate.
Preferably, in the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step B, the phosphorus source is phosphoric acid with a mass fraction of 80-90%.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step C, the template is at least one of tetraethylammonium hydroxide, triethylamine, diethylamine or morpholine.
Preferably, in the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step C, the template agent is triethylamine.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step D, the aging time is 0-20 hours.
Preferably, in the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step D, the aging time is 8-15 hours.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step D, the heating rate of heating for hydrothermal crystallization is 2-5 ℃/min, the temperature of the hydrothermal crystallization is 160-220 ℃, and the time of the hydrothermal crystallization is 24-48 h.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step E, the washing is as follows: and washing with water until the pH value of the material is 7-8.
In the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve, in the step E, the calcination is as follows: controlling the air flow to be 100-1000 mL/min, the calcining temperature to be 450-600 ℃, and the calcining time to be 2-10 h.
The invention also provides the properties of the low-cost hierarchical pore SAPO-34 molecular sieve prepared by the method, the particle size is 2-10 mu m, and the specific surface area is 20-300 m2A ratio of mesoporous particles to the total pore volume of the resin composition is 20 to 100% by weight3(iv)/g, the average pore diameter is 6.5 to 14.6 nm.
The invention also provides application of the SAPO-34 molecular sieve in the field of low-temperature denitration.
The invention has the beneficial effects that:
the invention carries out resource utilization on the lithium silicon powder which is a large number of piled up waste residues at present, and the lithium silicon powder is used as a silicon source and an aluminum source in the process of synthesizing the SAPO-34 molecular sieve, thereby providing a low-cost preparation method and having remarkable social benefit and economic benefit; most SAPO-34 molecular sieves prepared by a traditional hydrothermal method are of a microporous structure, and the limited molecular transfer rate and the large diffusion resistance of the SAPO-34 molecular sieves limit the industrial application of the SAPO-34 molecular sieves; according to the invention, by controlling the use amount of each material and optimizing the synthesis conditions, the SAPO-34 molecular sieve has a micro-mesoporous multi-level pore structure, so that the defect of a single microporous structure is effectively overcome; the SAPO-34 molecular sieve can be used as a carrier material of a low-temperature denitration catalyst, and the prepared catalyst has excellent low-temperature activity.
Detailed Description
Specifically, the preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve comprises the following steps:
A. washing, drying and sieving lithium silicon powder by acid to obtain powder;
B. uniformly mixing water and a phosphorus source to obtain a phosphorus source liquid;
C. mixing the powder obtained in the step A and the phosphorus source liquid obtained in the step B, adding a template agent under a stirring state, and uniformly mixing to obtain a mixed liquid;
D. c, aging the mixed solution obtained in the step C at room temperature, and heating for hydrothermal crystallization to obtain a crystallized solution;
E. and D, cooling, washing, filtering, drying and calcining the crystallization liquid obtained in the step D to obtain the low-cost hierarchical pore SAPO-34 molecular sieve.
The lithium silicon powder is industrial waste residue generated in the process of industrially producing lithium carbonate by calcining spodumene at high temperature, and about ten tons of lithium silicon powder are generated when one ton of lithium carbonate is processed and produced; according to statistics, the generation amount is huge. The silicon-aluminum content in the lithium silicon powder is higher, wherein the active SiO is2And Al2O3The total amount of the molecular sieve is not less than 65 percent, and the basic conditions for preparing the SAPO-34 molecular sieve are provided.
The waste lithium silicon powder contains active SiO for preparing SAPO-34 molecular sieve2And Al2O3The effective components also contain a large amount of impurities, and tests show that the effective components contain a large amount of impuritiesFirstly, acid washing is carried out to remove impurities, so that the synthesized molecular sieve has lower BET and lower crystallinity; therefore, the waste lithium silicon powder is washed by acid with the concentration of 1-5 mol/L to remove S, Fe, Ca, K and other impurities, and SiO in the powder after acid washing2And Al2O3Total mass of>80 percent; the acid may be hydrochloric acid, sulfuric acid or nitric acid. After acid washing, the lithium silicon powder may still contain a small amount of indissolvable substances or silicate-coated oxides such as iron, calcium and the like, but experiments show that the denitration performance of the molecular sieve is not influenced, so that the acid-washed lithium silicon powder is directly used for synthesizing the molecular sieve.
In the method, because of the active SiO in the lithium silicon powder of different waste residues2And Al2O3May be different, and therefore the amounts of lithium silicon powder, water, phosphorus source and templating agent (and aluminum source) are determined according to the amount of Al in the mixed solution of step C2O3、H3PO4、SiO2Triethylamine and H2The molar ratio of O is 1.0: 1.5-2.5: 0-1.5: 1-5: controlling by 30-100; in order to obtain the SAPO-34 molecular sieve with excellent denitration efficiency at low temperature, the adding amount of the lithium silicon powder in the step A, the water in the step B, the phosphorus source in the step B and the template in the step C is preferably determined according to the Al content in the mixed liquid in the step C2O3、H3PO4、SiO2Triethylamine and H2The molar ratio of O is 1.0: 1.8-2.2: 0.6-1.0: 2.7-3.3: 40-60. Wherein, the water can be distilled water, deionized water, ultrapure water and the like.
Because of the active SiO in the lithium silicon powder of different waste residues2And Al2O3May vary in content, and generally the silicon content is higher (SiO)2And Al2O3The molar ratio is generally about 2.5), so when the molecular sieve contains Al2O3When the content requirement is higher, Al in the lithium silicon powder may appear2O3And insufficient conditions. When Al is contained in lithium silicon powder2O3When the aluminum source is insufficient, the aluminum source needs to be supplemented in the step B and the mixture is uniformly mixed. The supplemental aluminum source may be, but is not limited to, one of pseudoboehmite, boehmite, alumina, aluminum hydroxide, alumina sol, or soluble aluminum saltOr a combination of several; preferably alumina.
In step B, the phosphorus source may be, but is not limited to, one or a combination of several of phosphoric acid, ammonium phosphate, phosphite or soluble metal phosphate; tests prove that when the phosphorus source is phosphoric acid with the mass fraction of 80-90%, the low-temperature denitration efficiency of the SAPO-34 molecular sieve is better.
In step C, the template agent may be, but is not limited to, tetraethylammonium hydroxide (TEAOH), triethylamine, diethylamine, or a combination of one or more of morpholine; tests prove that when the template agent is triethylamine, the low-temperature denitration efficiency of the SAPO-34 molecular sieve is better.
In the step D, the aging time is 0-20 h; but the denitration reaction effect after aging is better, and especially the denitration efficiency under the low-temperature condition is more excellent, so the aging time is preferably 8-15 h.
In the step D, the heating rate of the heating for the hydrothermal crystallization is 2-5 ℃/min, the temperature of the hydrothermal crystallization is 160-220 ℃, and the time of the hydrothermal crystallization is 24-48 h.
In step E, the washing is: washing with water until the pH value of the material is 7-8; the calcination is as follows: controlling the air flow to be 100-1000 mL/min, the calcining temperature to be 450-600 ℃, and the calcining time to be 2-10 h.
The low-cost hierarchical pore SAPO-34 molecular sieve prepared by the method has the particle size of 2-10 mu m and the specific surface area of 20-300 m2A ratio of mesoporous particles to the total pore volume of the resin composition is 20 to 100% by weight3(iv)/g, the average pore diameter is 6.5 to 14.6 nm.
The invention also provides application of the SAPO-34 molecular sieve in the field of low-temperature denitration; the method carries out resource utilization on the waste lithium silicon powder as a silicon source and an aluminum source in the process of synthesizing the SAPO-34 molecular sieve, and the obtained SAPO-34 molecular sieve has excellent conversion capacity on nitrogen oxides at the temperature of 200 ℃, particularly at the low temperature of 150 ℃, and the denitration efficiency can reach more than 95%.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Hair brushThe raw materials used in the following examples: active SiO in waste lithium silicon powder2And Al2O3The contents are 48 wt% and 18 wt%, respectively; h3PO4、Al2O3And triethylamine is analytically pure.
Example 1
Mix 4.16mLH3PO4Dissolving in 36mL deionized water, placing on a magnetic stirrer, stirring vigorously for 30min, adding 3.34gAl2O3And continuously and violently stirring for 90min, then slowly adding 4g of lithium silicon powder which is washed by 3mol/L hydrochloric acid and dried and sieved by a 200-mesh sieve, stirring for 60min, adding 16.64mL of template agent triethylamine, and intensively stirring for 90min to form uniform mixed liquor. The mixed solution is filled into a polytetrafluoroethylene lining, sealed in a stainless steel reaction kettle, aged at room temperature for 12h, heated to 200 ℃ at the speed of 2 ℃/min and kept for 24 h. And (3) after the reaction kettle is cooled, taking out the mixed solution, washing the mixed solution to be neutral by using deionized water, drying the mixed solution in a drying oven at 105 ℃ for 12 hours to obtain molecular sieve raw powder, calcining the raw powder in a 550 ℃ tubular furnace for 5 hours at the air flow rate of 30-300 mL/min to remove the template agent, and heating at the heating rate of 2 ℃/min to obtain the SAPO-34 molecular sieve.
Example 2
Mix 4.16mLH3PO4Dissolving in 36mL deionized water, placing on a magnetic stirrer, stirring vigorously for 30min, adding 3.89gAl2O3And continuously and violently stirring for 90min, then slowly adding 1g of lithium silicon powder which is washed by 3mol/L hydrochloric acid and dried and sieved by a 200-mesh sieve, stirring for 60min, adding 16.64mL of template agent triethylamine, and intensively stirring for 90min to form uniform mixed liquor. The mixed solution is filled into a polytetrafluoroethylene lining, sealed in a stainless steel reaction kettle, aged at room temperature for 12h, heated to 200 ℃ at the speed of 2 ℃/min and kept for 24 h. And (3) after the reaction kettle is cooled, taking out the mixed solution, washing the mixed solution to be neutral by using deionized water, drying the mixed solution in a drying oven at 105 ℃ for 12 hours to obtain molecular sieve raw powder, calcining the raw powder in a 550 ℃ tubular furnace for 5 hours at the air flow rate of 30-300 mL/min to remove the template agent, and heating at the heating rate of 2 ℃/min to obtain the SAPO-34 molecular sieve.
Example 3
Mix 4.16mLH3PO4Dissolving in 36mL deionized water, placing on a magnetic stirrer, stirring vigorously for 30min, adding 3.34gAl2O3And continuously and violently stirring for 90min, then slowly adding 4g of lithium silicon powder which is washed by 3mol/L hydrochloric acid and dried and sieved by a 200-mesh sieve, stirring for 60min, adding 16.64mL of template agent triethylamine, and intensively stirring for 90min to form uniform mixed liquor. The mixed solution is filled into a polytetrafluoroethylene lining, sealed in a stainless steel reaction kettle, aged at room temperature for 12 hours, heated to 200 ℃ at the speed of 2 ℃/min and kept for 48 hours. And (3) after the reaction kettle is cooled, taking out the mixed solution, washing the mixed solution to be neutral by using deionized water, and drying the mixed solution in a drying oven at 105 ℃ for 12 hours to obtain molecular sieve raw powder, wherein the raw powder is calcined in a 550 ℃ tubular furnace for 5 hours at the air flow rate of 30-300 mL/min to remove the template agent, and the temperature rise rate is 2 ℃/min to obtain the SAPO-34 molecular sieve, wherein the O content of the SAPO-34 molecular sieve is 56.9 wt%, the Si content is 17.4 wt%, the Al content is 18.2 wt%, the P content is 5.1 wt%, and the other content is 2.4 wt%.
Example 4
Mix 4.16mLH3PO4Dissolving in 36mL deionized water, placing on a magnetic stirrer, stirring vigorously for 30min, adding 3.34gAl2O3And continuously and violently stirring for 90min, then slowly adding 4g of lithium silicon powder which is washed by 3mol/L hydrochloric acid and dried and sieved by a 200-mesh sieve, stirring for 60min, adding 16.64mL of template agent triethylamine, and intensively stirring for 90min to form uniform mixed liquor. The mixed solution is filled into a polytetrafluoroethylene lining and sealed into a stainless steel reaction kettle, and the temperature is directly increased to 200 ℃ at the speed of 2 ℃/min without the room temperature aging step, and is kept for 24 hours. And (3) after the reaction kettle is cooled, taking out the mixed solution, washing the mixed solution to be neutral by using deionized water, drying the mixed solution in a drying oven at 105 ℃ for 12 hours to obtain molecular sieve raw powder, calcining the raw powder in a 550 ℃ tubular furnace for 5 hours at the air flow rate of 30-300 mL/min to remove the template agent, and heating at the heating rate of 2 ℃/min to obtain the SAPO-34 molecular sieve.
Example 5
5g of ammonium hydrogen phosphate is dissolved in 60mL of deionized water, the mixture is placed on a magnetic stirrer to be stirred vigorously for 30min, 3g of alumina sol is added, the mixture is stirred vigorously for 90min, then 5g of lithium silicon powder which is not pickled is slowly added, 18mL of template diethylamine is added after stirring for 60min, and uniform mixed liquor is formed after strong stirring for 90 min. The mixed solution is filled into a polytetrafluoroethylene lining, sealed in a stainless steel reaction kettle, aged at room temperature for 6 hours, heated to 200 ℃ at the speed of 2 ℃/min and kept for 18 hours. And (3) after the reaction kettle is cooled, taking out the mixed solution, washing the mixed solution to be neutral by using deionized water, drying the mixed solution in a drying oven at 105 ℃ for 12 hours to obtain molecular sieve raw powder, calcining the raw powder in a 500 ℃ tubular furnace for 5 hours at the air flow rate of 30-300 mL/min to remove the template agent, and heating at the heating rate of 2 ℃/min to obtain the SAPO-34 molecular sieve.
Example 6
1. Specific surface area and pore structure testing
The specific surface area and the pore structure of the SAPO-34 molecular sieve obtained in the example 1-3 are tested, and the results are shown in Table 1.
TABLE 1 specific surface area and pore structure of SAPO-34 molecular sieves obtained in examples 1 to 3
As can be seen from Table 1, SAPO-34 synthesized by lithium silicon powder has mesopores of more than 50%, which is more beneficial to the transmission of reactants and products in the pore channels of the molecular sieve, thereby being beneficial to the denitration reaction.
2. Denitration Activity test
The SAPO-34 molecular sieve prepared in the embodiment 1-5 is used as a denitration catalyst carrier, ferromanganese is used as an active component, and a denitration catalyst Mn-Fe/SAPO-34 is prepared.
The method for testing the denitration activity of the catalyst comprises the following steps: NH (NH)3The SCR reaction was carried out in a quartz glass reactor having an internal diameter of 10mm, the reactor having quartz sand in the middle for packing the catalyst particles. And (3) sieving the catalyst particles subjected to tabletting forming by a sieve of 10-20 meshes, and placing the catalyst particles on quartz sand in the center of the reactor. If not specifically stated, the catalyst loading height is 6cm, and the denitration activity isThe composition of the simulated smoke in the sexual test system is as follows: NO 450ppm, O25 vol.%, in N2As balance gas, NH3NO is 1.1, total gas flow is 157ml/min, and reaction space velocity (GHSV) is 2000h-1. N in the course of the experiment2、NO、O2、NH3、SO2The flow rate of the reactor is controlled by a mass flow meter, and the mixed gas enters the reactor after passing through a mixed gas cylinder. The water vapor is mixed with the simulated flue gas and flows through the deionized water with a certain temperature, the mixed flue gas is brought into the mixed gas and enters the reactor together, and the water vapor content entering the mixed gas is controlled by adjusting the temperature of the deionized water. NO and O at the outlet are measured by adopting a Gasboard3000 online infrared flue gas analyzer2、SO2The concentration of (c).
The reaction temperatures for the activity tests were 150 ℃, 175 ℃ and 200 ℃, and data were collected while maintaining stability for 2 hours at each test temperature. The formula for calculating the NO conversion rate, i.e. the denitration efficiency of the catalyst, is as follows:wherein NO conversion (%) is NO conversion,andinlet and outlet concentrations (ppm) of NO, respectively. The results are shown in Table 2.
TABLE 2 catalyst Denitrification reaction results
As can be seen from table 2, the SAPO-34 molecular sieves with different BET specific surface areas and different mesoporous rates obtained under different reaction conditions have different denitration effects, and example 3 with the highest mesoporous rate has the best denitration efficiency as found by combining the data in tables 1 and 2.
Claims (10)
1. The preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve is characterized by comprising the following steps: the method comprises the following steps:
A. washing, drying and sieving lithium silicon powder by acid to obtain powder;
B. uniformly mixing water and a phosphorus source to obtain a phosphorus source liquid;
C. mixing the powder obtained in the step A and the phosphorus source liquid obtained in the step B, adding a template agent under a stirring state, and uniformly mixing to obtain a mixed liquid;
D. c, aging the mixed solution obtained in the step C at room temperature, and heating for hydrothermal crystallization to obtain a crystallized solution;
E. and D, cooling, washing, filtering, drying and calcining the crystallization liquid obtained in the step D to obtain the low-cost hierarchical pore SAPO-34 molecular sieve.
2. The method for preparing the low-cost hierarchical pore SAPO-34 molecular sieve according to claim 1, wherein the method comprises the following steps: in the step A, at least one of the following items is satisfied:
the acid is at least one of hydrochloric acid, sulfuric acid or nitric acid;
the concentration of the acid is 1-5 mol/L;
active SiO in the lithium silicon powder2And Al2O3The total mass ratio of (A) is not less than 65%.
3. The method for preparing the low-cost hierarchical pore SAPO-34 molecular sieve according to claim 1, wherein the method comprises the following steps: adding the lithium silicon powder obtained in the step A, the water obtained in the step B, the phosphorus source obtained in the step B and the template agent obtained in the step C according to the adding amount of Al in the mixed liquid obtained in the step C2O3、H3PO4、SiO2Triethylamine and H2The molar ratio of O is 1.0: 1.5-2.5: 0-1.5: 1-5: controlling by 30-100; preferably 1.0: 1.8-2.2: 0.6-1.0: 2.7-3.3: 40-60.
4. The method for preparing the low-cost hierarchical pore SAPO-34 molecular sieve according to claim 3, wherein the method comprises the following steps: when Al is contained in lithium silicon powder2O3And when the aluminum source is insufficient, replenishing the aluminum source in the step B and uniformly mixing.
5. The method for preparing the low-cost hierarchical pore SAPO-34 molecular sieve according to claim 4, wherein the method comprises the following steps: the aluminum source is at least one of pseudo-boehmite, alumina, aluminum hydroxide, alumina sol or soluble aluminum salt; preferably alumina.
6. The method for preparing the low-cost hierarchical pore SAPO-34 molecular sieve according to claim 1, wherein the method comprises the following steps: at least one of the following is satisfied:
in the step B, the phosphorus source is at least one of phosphoric acid, ammonium phosphate salt, phosphite or soluble metal phosphate; preferably, the phosphoric acid with the mass fraction of 80-90 percent;
in the step C, the template agent is at least one of tetraethylammonium hydroxide, triethylamine, diethylamine or morpholine; triethylamine is preferred.
7. The method for preparing the low-cost hierarchical pore SAPO-34 molecular sieve according to claim 1, wherein the method comprises the following steps: in the step D, at least one of the following items is satisfied:
the aging time is 0-20 h; preferably 8-15 h;
the heating rate of heating for hydrothermal crystallization is 2-5 ℃/min, the temperature of hydrothermal crystallization is 160-220 ℃, and the time of hydrothermal crystallization is 24-48 h.
8. The preparation method of the low-cost hierarchical pore SAPO-34 molecular sieve according to any one of claims 1 to 7, wherein the method comprises the following steps: in step E, at least one of the following is satisfied:
the washing is as follows: washing with water until the pH value of the material is 7-8;
the calcination is as follows: controlling the air flow to be 100-1000 mL/min, the calcining temperature to be 450-600 ℃, and the calcining time to be 2-10 h.
9. The low-cost hierarchical pore SAPO-34 molecular sieve prepared by the method of any one of claims 1 to 8, wherein the molecular sieve is characterized in that: the particle size of the SAPO-34 molecular sieve is 2-10 mu m, and the specific surface area is 20~300m2A ratio of mesoporous particles to the total pore volume of the resin composition is 20 to 100% by weight3(iv)/g, the average pore diameter is 6.5 to 14.6 nm.
10. The application of the low-cost hierarchical pore SAPO-34 molecular sieve prepared by the method of any one of claims 1 to 8 in the field of low-temperature denitration.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN116328852A (en) * | 2021-12-23 | 2023-06-27 | 中国石油天然气股份有限公司 | Hydrogenation catalyst carrier and preparation method thereof |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101624191A (en) * | 2009-08-03 | 2010-01-13 | 南京工业大学 | Method for preparing 13 X molecular sieve by using lithium slag as raw materials |
CN103253681A (en) * | 2013-05-24 | 2013-08-21 | 南京工业大学 | Method for preparing Na-A/X or Na-A/X/P cocrystal molecular sieve through lithium slag hydrothermal synthesis |
CN107697925A (en) * | 2017-10-24 | 2018-02-16 | 中国科学院上海高等研究院 | A kind of synthetic method of the molecular sieves of multi-stage porous SAPO 34 |
CN108557838A (en) * | 2018-06-25 | 2018-09-21 | 陕西延长石油(集团)有限责任公司 | A kind of preparation method of aluminium silicophosphate molecular sieve |
CN109485062A (en) * | 2018-12-27 | 2019-03-19 | 中国矿业大学(北京) | A kind of low temperature preparation method of lithium slag base NaA molecular sieve |
CN110270308A (en) * | 2019-06-27 | 2019-09-24 | 四川大学 | A kind of adsorbent and preparation method thereof for sewage treatment |
CN110451518A (en) * | 2019-09-09 | 2019-11-15 | 中国矿业大学 | A method of SAPO-34 molecular sieve is synthesized using hectorite |
-
2020
- 2020-05-29 CN CN202010475250.6A patent/CN111659251A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101624191A (en) * | 2009-08-03 | 2010-01-13 | 南京工业大学 | Method for preparing 13 X molecular sieve by using lithium slag as raw materials |
CN103253681A (en) * | 2013-05-24 | 2013-08-21 | 南京工业大学 | Method for preparing Na-A/X or Na-A/X/P cocrystal molecular sieve through lithium slag hydrothermal synthesis |
CN107697925A (en) * | 2017-10-24 | 2018-02-16 | 中国科学院上海高等研究院 | A kind of synthetic method of the molecular sieves of multi-stage porous SAPO 34 |
CN108557838A (en) * | 2018-06-25 | 2018-09-21 | 陕西延长石油(集团)有限责任公司 | A kind of preparation method of aluminium silicophosphate molecular sieve |
CN109485062A (en) * | 2018-12-27 | 2019-03-19 | 中国矿业大学(北京) | A kind of low temperature preparation method of lithium slag base NaA molecular sieve |
CN110270308A (en) * | 2019-06-27 | 2019-09-24 | 四川大学 | A kind of adsorbent and preparation method thereof for sewage treatment |
CN110451518A (en) * | 2019-09-09 | 2019-11-15 | 中国矿业大学 | A method of SAPO-34 molecular sieve is synthesized using hectorite |
Non-Patent Citations (3)
Title |
---|
张菊 等: "SAPO-34分子筛形貌和粒径的影响因素考察", 《工业催化》 * |
朱洪法 主编: "《催化剂手册》", 31 August 2008, 金盾出版社 * |
淡保松 等: "SAPO-34分子筛的合成", 《工业催化》 * |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN113371728B (en) * | 2021-07-09 | 2023-03-24 | 景德镇陶瓷大学 | Preparation method for rapidly synthesizing molecular sieve with hierarchical pore structure and product prepared by preparation method |
CN116328852A (en) * | 2021-12-23 | 2023-06-27 | 中国石油天然气股份有限公司 | Hydrogenation catalyst carrier and preparation method thereof |
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Application publication date: 20200915 |