CN108862309B - NaY molecular sieve aggregate with nano-micro structure and preparation method thereof - Google Patents
NaY molecular sieve aggregate with nano-micro structure and preparation method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 124
- 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 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 66
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 34
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- 239000000499 gel Substances 0.000 claims description 72
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- 239000000741 silica gel Substances 0.000 claims description 54
- 229910002027 silica gel Inorganic materials 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000011148 porous material Substances 0.000 claims description 39
- 229910052710 silicon Inorganic materials 0.000 claims description 35
- 239000010703 silicon Substances 0.000 claims description 35
- 229910001868 water Inorganic materials 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 32
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 29
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims description 28
- 229960004029 silicic acid Drugs 0.000 claims description 28
- 229960001866 silicon dioxide Drugs 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- 235000019353 potassium silicate Nutrition 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 239000007787 solid Substances 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
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 claims 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000013078 crystal Substances 0.000 abstract description 11
- 238000003756 stirring Methods 0.000 description 33
- 230000000694 effects Effects 0.000 description 27
- 238000005303 weighing Methods 0.000 description 21
- 239000002994 raw material Substances 0.000 description 11
- -1 KY and NH Chemical compound 0.000 description 10
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 229950011008 tetrachloroethylene Drugs 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 239000002149 hierarchical pore Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 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 2
- 239000000463 material Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241001522296 Erithacus rubecula Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Abstract
The invention provides a NaY molecular sieve aggregate with a nano-micro structure and a preparation method thereof. The method comprises the following steps: synthesizing a guiding agent; preparing a reaction gel by using the guiding agent; crystallizing the reaction gel to obtain a NaY molecular sieve aggregate with a nano-micro structure; wherein, the organosilicon quaternary ammonium salt is introduced in the process of synthesizing the directing agent and/or preparing the reaction gel. The technical scheme provided by the invention has the advantages of simple process and lower cost, and the finally obtained product has a series of advantages of complete crystal phase, high silicon-aluminum ratio, high specific surface area, rich mesoporous-microporous structure, controllable crystal grain size and the like.
Description
Technical Field
The invention relates to a NaY molecular sieve aggregate with a nano-micro structure and a preparation method thereof, belonging to the technical field of molecular sieve preparation.
Background
The Y-type molecular sieve is widely applied to the industry due to the special three-dimensional pore channel structure, high-temperature stability and good catalytic activity. At the end of the 50 s, MILTON R.M. and BRECK D.W. (US3130007) successfully synthesized Y-type molecular sieves. The Y-type molecular sieve substitutes X-type zeolite with high stability, high activity, metal pollution resistance and sintering resistance to become the main active component of the catalyst. In the early 70 s, the NaY molecular sieve was synthesized by GRACE (US 3639099, US 3671191) by a guiding agent method, and water glass was used as a raw material to replace expensive silica sol, so that the process is simplified, and the production period is shortened, thereby the NaY molecular sieve is rapidly and widely applied to the field of petroleum catalytic cracking.
The conventional method for industrially producing the NaY molecular sieve at present adopts water glass as a raw material to prepare mixed glue, and the synthesis of the Y-type molecular sieve is completed by crystallization. Because the raw materials of the water glass system contain a large amount of water, wherein the mass fraction of silicon dioxide is only 19-28%, and the viscosity of a synthesis system is high, so that the solid content of the system cannot be increased, the solid content of the method is low, the yield of a single kettle for preparing the Y-type molecular sieve in each reaction process is lower than 10-12%, the utilization rate of a silicon source is low, the loss of the silicon source is serious, and a large amount of alkali liquor containing silicon is generated to cause harm to the environment. According to the report, most processes recycle mother liquor for preparing the Y-type molecular sieve for multiple times, so that a large amount of silicon source loss in the processes is compensated to a certain extent, but complexity of the Y-type molecular sieve preparation process and uncontrollable product properties are brought invisibly.
The synthesis research of the Y-type molecular sieve mainly focuses on the following two aspects:
first, from the viewpoint of improving product performance. The NaY type molecular sieve is widely used in industry with high stability and good catalytic activity. Obtaining other forms of Y-type molecular sieve, such as KY and NH, by ion exchange or other modification method4Y, USY, REY, HY, REUSY and the like have been well applied to the fields of petroleum refining and the like. As an active component or a carrier of the catalyst, the grain size of the molecular sieve, the content of sodium ions in the molecular sieve, the framework silicon-aluminum ratio, the unit cell parameter of the molecular sieve and the pore structure in the molecular sieve influence the performance of the molecular sieve in the catalyst. For example, the molecular sieve with high silica-alumina ratio can improve the framework silica-alumina of the modified molecular sieve, and has higher hydrothermal stability and crystallinity retention degree; the small-crystal-grain molecular sieve can improve the catalytic selectivity, reduce the formation of coke, increase the yield of diesel oil and improve the quality of gasoline; the hierarchical pore molecular sieve has a highly communicated pore structure, and can improve the reaction rate, selectivity, lower inactivation rate and new adsorption capacity.
Secondly, from the perspective of high efficiency, economy and environmental protection, how to synthesize a high-quality Y molecular sieve under the conditions of improving the yield of a single kettle, increasing the utilization rate of a silicon source and reducing pollutant emission becomes one of the efforts of researchers under the continuous improvement of a NaY molecular sieve synthesis process.
Therefore, it becomes a hot point of research to develop an efficient synthesis system and process to prepare a high-performance Y-type molecular sieve with good crystallinity, high silicon-aluminum ratio, controllable grain size and hierarchical pore structure.
The hydrothermal dealumination process proposed by McDaniel (Society of Chemical Industry, London.1968:186) et al in 1967 has been developed to date for fifty years. In the method, in the process of ultrastabilizing the zeolite framework, mesopores are introduced into the zeolite framework through dealuminization of the zeolite framework, so that the molecular sieve with high silica-alumina ratio and rich mesopores is obtained.
In 1983, Breck d.w. and Skeels G.W (US4503023) invented a method for liquid phase dealumination and silicon supplementation modification of Y-type zeolite with ammonium fluorosilicate. In 1980, Beyer et al first reported isomorphous substitution of aluminum atoms in the zeolite framework with silicon tetrachloride in a gas phase environment (Studies in Surface Science and catalysis. Elsevier,1980: 203-. Under proper conditions, the obtained product has the advantages of higher framework silica-alumina ratio and complete structure, but fewer generated intracrystalline mesopores. Other chemical dealumination methods have been reported mainly for EDTA complexation dealumination (Catalysis letters.1993,19(2-3): 159. 165.) and for dealumination of citric acid (Journal of catalysis.2011,279(1): 27-35).
In 2010, Chal.Robin et al (Chemical Communications,2010.46(41): p.7840.) treated HY in a solution containing TMAOH and CTAB, the total pore volume was from 0.4cm3g-1Increased to 0.6cm3g-1The volume of the micropore is 0.19cm3g-1Halving, increasing the mesoporous volume to 0.51cm3g-1. Then, the author[80]It is pointed out that the method can also be applied to molecular sieves with lower silicon-aluminum atomic ratio (2.5-3.0), which are pretreated with diluted acid solution.
In 2010, Yi Huang et al (Microporous and Mesoporous Materials,2010.127(3): p.167-175.) synthesized a hierarchical pore Y-type molecular sieve (190- & 600nm) with small crystal grain (20-80nm) accumulation in a hydrothermal system by three-step temperature control (stirring at room temperature for 24h, aging at 38 ℃ for 24h, and 60 crystallization for 48h), and the size of the crystal grain is controlled by adjusting the water content.
In 2013, researchers (Microporous and Mesoporous materials.2013,170: 243-. This recrystallization process consists in treating the molecular sieve crystals in an alkaline solution in the presence of a surfactant. The method is shown in previous researches to be capable of generating uniform mesoporous distribution inside molecular sieve crystals and taking the Y-type molecular sieve as a model, and the original shape of the molecular sieve can be reserved.
In 2011, CN102689910A adopts trimethylsilyl modified polymer as a template agent, and adopts a sol-gel method to synthesize the mesoporous and microporous Y-type molecular sieve in a hydrothermal system. The pore size of mesopores generated on the molecular sieve in the synthesis process can be adjusted by changing the molecular weight of the co-template.
In 2013, CN103214003A uses amphiphilic organosilane N, N-dimethyl-N- [3- (trimethoxy) propyl ] octadecyl ammonium chloride (TPOAC) as a mesoporous template to guide the synthesis of a mesoporous Y molecular sieve in a one-step hydrothermal system.
In 2013, CN103043680A provides all silicon sources and aluminum sources for molecular sieve synthesis by using natural kaolin minerals and natural diatomite minerals, and the natural kaolin minerals and the natural diatomite minerals are used as substrates for molecular sieve growth, and NaY molecular sieve/natural mineral composite materials with multilevel structures are formed through in-situ crystallization, but the molecular sieves obtained in the way and the substrates are mixed to obtain products.
In 2014, CN104891523A adopts a mesoporous-containing Y molecular sieve synthesized by an organic template agent, the mesoporous Y molecular sieve is further used as a seed crystal to be added into a synthesis system of the Y molecular sieve, and a guiding agent is combined in the synthesis process to prepare the mesoporous molecular sieve. Thus, the preparation system indirectly uses a small amount of organic template agent to synthesize the mesoporous Y molecular sieve.
In summary, the conventional synthetic dielectric structure Y molecular sieve is prepared by using water glass as a raw material and modifying synthetic gel in a hydrothermal system, and has the problems of large material consumption of a template agent, low product yield, mother liquor discharge and the like.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a NaY molecular sieve aggregate with a nano-micro structure and a preparation method thereof. The technical scheme provided by the invention has the advantages of simple process and lower cost, and the finally obtained product has a series of advantages of complete crystal phase, high silicon-aluminum ratio, high specific surface area, rich mesoporous-microporous structure, controllable crystal grain size and the like.
In order to achieve the above object, the present invention provides a method for preparing NaY molecular sieve aggregates with nano-and micro-structures, comprising the following steps:
synthesizing a guiding agent;
preparing a reaction gel by using the guiding agent;
crystallizing the reaction gel to obtain a NaY molecular sieve aggregate with a nano-micro structure; wherein the content of the first and second substances,
the organosilicon quaternary ammonium salt is introduced in the process of synthesizing the directing agent and/or preparing the reaction gel.
According to the technical scheme provided by the invention, the organic silicon quaternary ammonium salt is introduced into the guiding agent and/or the reaction gel to obtain the guiding agent with high regularity and/or the hydrated silica gel with high regularity.
According to the technical scheme provided by the invention, the organic silicon quaternary ammonium salt is adopted to carry out silanization modification on the guiding agent or reaction gel for synthesizing the Y molecular sieve, and the NaY molecular sieve ordered aggregate with the nano-microstructure is synthesized in a high-concentration system, so that the single-kettle yield and the single-kettle utilization rate are improved, the performance of the product is improved, the finally prepared product has the characteristics of nano-crystal grains and hierarchical pores formed by the nano-crystal grains, and the difficult problem of molecular sieve nano-crystal separation engineering caused by the formed aggregate is solved.
In the above method, preferably, synthesizing the directing agent comprises the following processes: according to Na2O:Al2O3:SiO2:H2O, QASCs (15-25), 1 (8-30), 250 (450) and 0-10, and uniformly mixing a silicon source, water, an alkali source, an aluminum source and an organosilicon quaternary ammonium salt, and aging to prepare a directing agent; wherein the organosilicon quaternary ammonium salt is represented by QASCs; more preferably, the guiding agent is synthesized by feeding Na in a molar ratio2O:Al2O3:SiO2:H2QASCs (15-25), 1 (8-30), 250 (450) and 0-5. In synthesizing the directing agent, the water in the molar ratio is fed from the water in the silicon source and the additional water (the additional water includes deionized water).
In the above method, preferably, the step of uniformly mixing the silicon source, the water, the alkali source, the aluminum source and the organosilicon quaternary ammonium salt in the step of synthesizing the directing agent comprises the following steps: mixing a silicon source and an alkali source for pretreatment; then adding water, an aluminum source and the organosilicon quaternary ammonium salt into the mixture, and uniformly mixing.
In the above method, preferably, the silicon source used in the synthesis of the directing agent comprises water glass and/or silica sol.
In the above method, preferably, the aluminum source used in the synthesis of the directing agent comprises one or a combination of sodium metaaluminate, aluminum sulfate and aluminum nitrate.
In the above method, preferably, the alkali source suitable for use in the synthesis of the directing agent comprises sodium hydroxide.
In the above method, preferably, the water used in the synthesis of the directing agent is deionized water.
In the above method, the aging may be performed by using an existing aging operation means during the synthesis of the directing agent, and preferably, the aging temperature is 0 to 40 ℃, more preferably 10 to 30 ℃; the aging time is 5 to 100 hours, more preferably 15 to 60 hours.
In the above method, preferably, the preparation of the reaction gel using the directing agent comprises the following processes:
according to Na2O:Al2O3:SiO2:H2QASCs (2-6) and (1) (5.5-10.5) and (50-150) (0-5.0) in the total feeding molar ratio, and uniformly mixing a silicon source, water, an aluminum source, a directing agent and organosilicon quaternary ammonium salt to prepare reaction gel; wherein the organosilicon quaternary ammonium salt is represented by QASCs. It is understood that the number of moles in the total charge molar ratio in the preparation of the reaction gel refers to the total number of moles of synthesis directing agent + total charge in the preparation of the reaction gel.
In the above method, preferably, the total charge molar ratio in the preparation of the reaction gel by using the directing agent is Na2O:Al2O3:SiO2:H2O:QASiCs＝(2.5-4):1:(7-9):(85-120):(0-2.0)。
In the above method, preferably, the silicon source used in the reaction gel preparation process includes one or a combination of several of water glass, C-type silica gel, sodium silicate and white carbon black; more preferably, the silicon source is a solid.
In the above method, preferably, the aluminum source used in the preparation of the reaction gel comprises one or a combination of sodium metaaluminate, aluminum sulfate and aluminum nitrate.
In the above method, preferably, the water used in the preparation of the reaction gel is deionized water.
In the above method, preferably, the step of uniformly mixing the silicon source, the water, the aluminum source, the directing agent and the organosilicon quaternary ammonium salt in the step of preparing the reaction gel comprises the following steps: adding a silicon source into water for pretreatment to prepare hydrated silica gel; adding an aluminum source, a guiding agent and an organosilicon quaternary ammonium salt into the hydrated silica gel; more preferably, when the silicon source is added into water for pretreatment, the pretreatment temperature is 0-60 ℃, and the pretreatment time is 2-4 h.
In the above method, preferably, the H introduced by adding water is used in preparing the reaction gel2The weight of O is 30-80%, more preferably 30-50% of the total weight of the reaction gel.
In the above method, preferably, Al introduced by adding a directing agent is added at the time of preparing the reaction gel2O3Is based on the weight of Al in the reaction gel2O35-20% of the total weight.
In the above method, preferably, the SiO introduced by adding the silicone quaternary ammonium salt is used in preparing the reaction gel2In the reaction gel of SiO20.1 to 15% by weight, more preferably 0.1 to 10% by weight, based on the total weight.
In the above method, preferably, the silicone quaternary ammonium salt introduced during the synthesis of the directing agent and/or the preparation of the reaction gel comprises one or a combination of N, N-dimethyl-N-dodecylaminopropylalkoxysilane quaternary ammonium salt, N-dimethyl-N-tetradecylaminopropylalkoxysilane quaternary ammonium salt and N, N-dimethyl-N-hexadecylaminopropylalkoxysilane quaternary ammonium salt.
In the above method, preferably, the synthesis directing agent and/or the organosilicon quaternary ammonium salt introduced during the preparation of the reaction gel comprises one or more of the compounds with the structure shown in formula 1
[(CnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1]X formula 1
In formula 1, n is 1 or 2; x is 12, 14 or 16; x is Cl, Br or I.
In the above method, the crystallization of the reaction gel may be performed by a conventional crystallization operation in the art, and preferably, the crystallization of the reaction gel comprises the following steps: crystallizing the reaction gel at 90-110 ℃ for 20-120 h; after crystallization, filtering, washing and drying; more preferably, the crystallization time is 24-72 h.
In a preferred embodiment, the method for preparing NaY molecular sieve aggregates with nano-and microstructures comprises the following steps:
according to Na2O:Al2O3:SiO2:H2O, QASCs (15-25), 1 (8-30), 250 (450) and 0-10, and uniformly mixing a silicon source, water, an alkali source, an aluminum source and an organosilicon quaternary ammonium salt, and aging to prepare a directing agent; wherein the organosilicon quaternary ammonium salt is represented by QASCs;
according to Na2O:Al2O3:SiO2:H2O, QASCs (2-6) is 1, (5.5-10.5) to (50-150) to (0-5.0), a silicon source is added into water for pretreatment to prepare hydrated silica gel, an aluminum source, a guiding agent and organosilicon quaternary ammonium salt are sequentially added into the hydrated silica gel, and the mixture is uniformly mixed to prepare reaction gel; wherein the organosilicon quaternary ammonium salt is represented by QASCs;
crystallizing the reaction gel to obtain a NaY molecular sieve aggregate with a nano-micro structure; wherein the content of the first and second substances,
when the guiding agent and the reaction gel are prepared, the introduced organosilicon quaternary ammonium salt is not 0 at the same time.
The invention also provides the NaY molecular sieve aggregate with the nano-micro structure, which is prepared by the method and has the characteristics of micropores and mesopores. The overall size of the NaY molecular sieve aggregate is 1-5 μm, preferably 2-4 μm, and the NaY molecular sieve aggregate is formed by orderly aggregating nano-micron crystals, wherein the size of the nano-micron crystals is preferably 5-100nm, and more preferably 10-100 nm.
In the NaY molecular sieve aggregate described above, preferably, the silicon-aluminum ratio of the NaY molecular sieve aggregate is 4.0 to 6.0; the pore volume is 0.3-0.6cm3(ii)/g; the external specific surface area is 50-180m2A/g, more preferably 80 to 140m2(ii)/g; BET specific surface area of 650-750m2(ii)/g, more preferably 680-750m2/g。
In the NaY molecular sieve aggregate described above, preferably, the relative crystallinity of the NaY molecular sieve aggregate is 95% to 100%.
In the technical scheme provided by the invention, the water glass can adopt a conventional reagent, such as SiO228.08 wt% of Na2A commercially available water glass product having an O content of 8.83 wt%; the silica sol can be prepared by using a commercially available conventional reagent, for example, SiO240.00 wt% of Na2A commercially available silica sol product having an O content of 0.40 wt% and an average size of 10 to 20 nm; the C-type silica gel (also called coarse pore silica gel) can adopt a conventional product sold in the market, such as the pore volume is more than or equal to 0.78cm3Per g of commercially available C-type silica gel; in addition, the white carbon black can also adopt conventional chemical reagents sold in the market.
In the technical scheme provided by the invention, the organosilane quaternary ammonium salt can be synthesized according to the following method: mixing silane and tertiary amine according to the proportion of (1:1) - (1:3), and reacting for 24-60h at 40-80 ℃ to prepare organosilicon quaternary ammonium salt; among them, silane and tertiary amine may be conventional ones in the art, and are not particularly limited, and for example, commercially available chloropropyltriethoxysilane having a chloropropyltriethoxysilane content of 98.00% and commercially available dodecyltertiary amine having a dodecyltertiary amine content of 97% may be used.
The invention has the beneficial effects that:
1) according to the technical scheme provided by the invention, an organosilane quaternary ammonium salt is adopted to modify and modify a guiding agent and/or reaction gel for synthesizing the Y molecular sieve, and a NaY molecular sieve aggregate ordered aggregate with a nano-microstructure is synthesized in a high-concentration system, so that the yield of a single kettle and the utilization rate of the single kettle are improved on one hand, the performance of a product is improved on the other hand, the finally synthesized product has the characteristics of small grains and hierarchical pores, and the formed aggregate solves the difficult problem of nanocrystalline separation engineering of the molecular sieve, so that a new thought and direction are provided for the synthesis and application of the nanocrystalline Y molecular sieve;
2) according to the technical scheme provided by the invention, the organic silicon quaternary ammonium salt is introduced into the guiding agent and/or the reaction gel to obtain the guiding agent with high regularity and/or the hydrated silica gel with high regularity, and the finally obtained product has a series of advantages of complete crystalline phase, high silica-alumina ratio, high specific surface area, rich mesoporous-microporous structure, controllable grain size and the like;
3) the technical scheme provided by the invention has the advantages of simple process and lower cost, and can synthesize the NaY molecular sieve aggregate containing mesopores and micropores and having uniform size, wherein the silicon-aluminum ratio of the NaY molecular sieve aggregate is 4.0-6.0, the grain size is 5-100nm, the particle size of the Y molecular sieve aggregate is 1-5 mu m, and the pore volume is 0.3-0.6cm3(ii)/g; the external specific surface area and the total pore volume of the NaY molecular sieve aggregate are greatly improved (can be improved by more than 50%) compared with the molecular sieve synthesized by a hydrothermal system, the grain size of the NaY molecular sieve aggregate is below 100nm, and the characteristics can obviously improve the catalytic reaction performance of the product and the utilization rate of the molecular sieve; (ii) a
4) Compared with the prior art, the technical scheme provided by the invention can introduce less template agent through the modification guiding agent on the basis of modifying gel, thereby more efficiently regulating and controlling the grain size and the pore structure of the synthesized product; in addition, according to the technical scheme provided by the invention, when the reaction gel is prepared, the solid silicon source is adopted, so that the yield of the product can be greatly improved, and the method is energy-saving and environment-friendly.
Drawings
FIG. 1 is an XRD pattern of the NaY molecular sieve aggregate provided in example 1 and the NaY molecular sieve provided in comparative example 1;
FIG. 2 is an SEM photograph of NaY molecular sieve aggregates provided in example 1;
FIG. 3 is an SEM picture of NaY molecular sieve aggregates provided in comparative example 1;
FIG. 4 shows the NaY molecular sieve aggregate provided in example 1 and comparative example 1N of NaY molecular sieve2Adsorption-desorption curve.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a preparation method of a NaY molecular sieve aggregate with a nano-microstructure, which comprises the following steps:
1) 57.81g of water glass (SiO in water glass) are weighed2Has a content of 28.08 wt% and Na2The content of O is 8.83wt percent) is placed in a beaker, 8.81g of sodium hydroxide solid (analytically pure, Beijing century Hongxing chemical Co., Ltd.) is weighed and placed in the beaker, the two are mixed and stirred uniformly, and stirred for 2 hours at room temperature (27 ℃) to prepare a high-activity hydrated sodium silicate solution;
then, 54.11g of deionized water and 3.12g of sodium metaaluminate (All, chemical research institute of Otsujin, Otsumadam, Ltd.) were sequentially added2O3Is 45 wt% of Na2The content of O is 41wt percent), evenly stirred and mixed, and added with 3g N, N-dimethyl-N-hexadecylaminopropyl silane quaternary ammonium salt [ (C)nH2n+1O)3SiC3H6N(CH3)2-CxH2x+1]X, wherein n ═ 1; x is 16; x ═ Cl) and aged at room temperature (27 ℃) for 36 hours to prepare the directing agent.
TABLE 1
| Example 1 | Comparative example 1 | |
| Silicon source in directing agent | Water glass | Water glass |
| Silicon source in reaction gel | Solid silica gel | Solid silica gel |
| Specific surface area/(m)2/g) | 683.00 | 689.20 |
| External specific surface area/(m)2/g) | 122.80 | 26.80 |
| Mesopore pore volume/(cm)3/g) | 0.16 | 0.06 |
| Silicon to aluminum ratio | 5.6 | 5.30 |
| Grain size/nm | 20-100 | 200-800 |
| Overall shape/size | Aggregate (1-4 μm) | -- |
2) 42.54g of C-type silica gel (also called coarse-pore microspherical silica gel) is weighed and added into 90g of deionized water, stirred for 3 hours at constant temperature of 20 ℃ to prepare high-activity hydrated silica gel, then 21.00g of sodium metaaluminate is weighed and added into the high-activity hydrated silica gel after being uniformly stirred, 83.38g of the guiding agent is added, and the reaction gel is prepared after being uniformly stirred.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, statically crystallizing at 100 ℃ for 48 hours, and then filtering, washing and drying to obtain a NaY molecular sieve aggregate product.
The BET specific surface area of the NaY molecular sieve aggregate product provided in the embodiment is 683m2The silicon-aluminum ratio is 5.6, the grain size is 20-100nm, the aggregate size is 1-4 μm, and the pore volume is 0.46cm3/g。
The physicochemical properties and the preparation process of the NaY molecular sieve aggregate provided in this example are analyzed in table 1, the XRD spectrogram of the product is shown in fig. 1, the electron microscopy spectrogram is shown in fig. 2, and N is2The adsorption-desorption curve is shown in fig. 4.
Example 2
The embodiment provides a preparation method of a NaY molecular sieve aggregate with a nano-microstructure, which comprises the following steps:
1) the preparation method and raw material source of the directing agent are the same as those of example 1.
2) 32.54g of C-type silica gel (also called coarse-pore microspherical silica gel) is weighed and added into 50g of deionized water, 53.19g of water glass is added, stirring is carried out for 3 hours at constant temperature of 20 ℃, high-activity hydrated silica gel is prepared, and then 15.00g of sodium metaaluminate and 17.64g of aluminum sulfate (Tianjin, Guangzhi technology development Co., Ltd., Al2SO4·18H2The content of O is 99 percent) is dissolved in high-activity hydrated silica gel, and after being uniformly stirred, 83.38g of the guiding agent is added and is uniformly stirred to prepare reaction gel.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, statically crystallizing at 100 ℃ for 48 hours, and then filtering, washing and drying to obtain a NaY molecular sieve aggregate product.
The BET specific surface area of the NaY molecular sieve aggregate product provided in this example is 662m2The silicon-aluminum ratio is 5.3, the grain size is 20-100nm, the aggregate size is 1-4 μm, and the pore volume is 0.39cm3/g。
Example 3
The embodiment provides a preparation method of a NaY molecular sieve aggregate with a nano-microstructure, which comprises the following steps:
1) the preparation method and raw material source of the directing agent are the same as those of example 1.
2) Weighing 40.54g of coarse-pore microspherical silica gel, adding the coarse-pore microspherical silica gel into 86g of deionized water, stirring for 3 hours at constant temperature of 20 ℃ to prepare high-activity hydrated silica gel, weighing 20.00g of sodium metaaluminate into the high-activity hydrated silica gel, uniformly stirring, adding 83.38g of the guiding agent, and uniformly stirring to prepare reaction gel.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, statically crystallizing for 96 hours at 100 ℃, and then filtering, washing and drying to obtain a NaY molecular sieve aggregate product.
The specific surface area of the NaY molecular sieve aggregate product provided by the embodiment is 693m2The silicon-aluminum ratio is 5.6, the grain size is 60-100nm, the aggregate size is 1-4 μm, and the pore volume is 0.53cm3/g。
Example 4
The embodiment provides a preparation method of a NaY molecular sieve aggregate with a nano-microstructure, which comprises the following steps:
1) the sources of the various raw materials were the same as in example 1
Weighing 55.80g of water glass and placing the water glass in a beaker, weighing 9.66g of sodium hydroxide solid and placing the sodium hydroxide solid in the beaker, mixing and stirring the two materials uniformly, and stirring the mixture for 1 hour at room temperature (20 ℃) to prepare a high-activity sodium silicate hydrate solution; 47.39g of deionized water and 2.82g of sodium metaaluminate are sequentially added, stirred and mixed uniformly, and aged at 15 ℃ for 120 hours to prepare the directing agent.
2) Weighing 20.31g of coarse-pore microspherical silica gel, adding the coarse-pore microspherical silica gel into ionized water, stirring for 3 hours at constant temperature of 40 ℃ to prepare high-activity hydrated silica gel, weighing 10.00g of sodium metaaluminate into the high-activity hydrated silica gel, uniformly stirring, adding 37.65g of the guiding agent, and uniformly stirringHomogenizing, and adding 3.5g N, N-dimethyl-N-hexadecylaminopropylsilane quaternary ammonium salt ([ (C)nH2n+1O)3SiC3H6N(CH3)2-CxH2x+1]X, wherein n ═ 1; x is 16; x ═ Cl), a reaction gel was prepared.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, statically crystallizing for 72 hours at 100 ℃, and then filtering, washing and drying to obtain a NaY molecular sieve aggregate product.
The BET specific surface area of the NaY molecular sieve aggregate provided in the example is 683m2The silicon-aluminum ratio is 5.24, the grain size is 20-100nm, the aggregate size is 1-3 μm, and the pore volume is 0.42cm3/g。
Example 5
The embodiment provides a preparation method of a NaY molecular sieve aggregate with a nano-microstructure, which comprises the following steps:
1) the preparation method and raw material source of the directing agent are the same as those of example 4.
2) Weighing 20.31g of coarse-pore microspherical silica gel, adding the coarse-pore microspherical silica gel into ionized water, stirring for 3 hours at constant temperature of 20 ℃ to prepare high-activity hydrated silica gel, then weighing 10.00g of sodium metaaluminate into the high-activity hydrated silica gel, stirring uniformly, adding 37.65g of the guiding agent, stirring uniformly, and then adding 4.5g N, N-dimethyl-N-hexadecylaminopropylsilane quaternary ammonium salt ([ (C)nH2n+1O)3SiC3H6N(CH3)2-CxH2x+1]X, wherein n ═ 1; x is 16; x ═ Br), a reaction gel was prepared.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, statically crystallizing for 72 hours at 100 ℃, and then filtering, washing and drying to obtain a NaY molecular sieve aggregate product.
The BET specific surface area of the NaY molecular sieve aggregate provided in this example is 703m2The silicon-aluminum ratio is 5.34, the grain size is 20-100nm, the aggregate size is 1-3 μm, and the pore volume is 0.40cm3/g。
Example 6
The embodiment provides a preparation method of a NaY molecular sieve aggregate with a nano-microstructure, which comprises the following steps:
1) the preparation method and raw material source of the directing agent are the same as those of example 4.
2) Weighing 20.31g of coarse-pore microspherical silica gel, adding the coarse-pore microspherical silica gel into ionized water, stirring for 3 hours at constant temperature of 20 ℃ to prepare high-activity hydrated silica gel, then weighing 10.00g of sodium metaaluminate into the high-activity hydrated silica gel, stirring uniformly, adding 37.65g of the guiding agent, stirring uniformly, and then adding 4.0g N, N-dimethyl-N-dodecylaminopropyl silane quaternary ammonium salt ([ (C)nH2n+1O)3SiC3H6N(CH3)2-CxH2x+1]X, wherein n ═ 1; x is 12; x ═ Cl), a reaction gel was prepared.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, statically crystallizing for 72 hours at 100 ℃, and then filtering, washing and drying to obtain a NaY molecular sieve aggregate product.
The specific surface area of the NaY molecular sieve aggregate provided by the embodiment is 675m2The silicon-aluminum ratio is 5.21, the grain size is 20-100nm, the aggregate size is 1-2 μm, and the pore volume is 0.41cm3/g。
Example 7
The embodiment provides a preparation method of a NaY molecular sieve aggregate with a nano-microstructure, which comprises the following steps:
the sources of the various starting materials were the same as in example 1.
1) Weighing 74.40g of water glass, placing the water glass in a beaker, weighing 11.21g of sodium hydroxide solid, placing the sodium hydroxide solid and the beaker, mixing and stirring the two uniformly, and stirring the mixture for 4 hours at 18 ℃ to prepare a high-activity sodium silicate hydrate solution; 62.95g of deionized water, 5.27g of sodium metaaluminate, 3.40. 3.40g N, N-dimethyl-N-tetradecylaminopropylsilane quaternary ammonium salt ([ (C)nH2n+1O)3SiC3H6N(CH3)2-CxH2x+1]X, wherein n ═ 1; x is 14; x ═ Cl), stirring and mixing homogeneously, aging at 24 ℃ for 72 hours to obtainA directing agent.
2) Weighing 22.28g of coarse-pore microspherical silica gel, adding the coarse-pore microspherical silica gel into deionized water, stirring for 3 hours at constant temperature of 30 ℃ to prepare high-activity hydrated silica gel, weighing 11.00g of sodium metaaluminate into the high-activity hydrated silica gel, uniformly stirring, adding 43.68g of the guiding agent, and uniformly stirring to prepare reaction gel.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, crystallizing at 100 ℃ for 60 hours, and then filtering, washing and drying to obtain a NaY molecular sieve aggregate product.
The specific surface area of the NaY molecular sieve aggregate provided in the example is 645m2The silicon-aluminum ratio is 5.47, the grain size is 60-100nm, the aggregate size is 3-5 μm, and the pore volume is 0.40cm3/g。
Example 8
The various sources of starting materials were the same as in example 1.
1) Weighing 55.80g of water glass, placing the water glass in a beaker, weighing 9.66g of sodium hydroxide solid in the beaker, mixing and stirring the water glass and the sodium hydroxide solid uniformly, and stirring the mixture for 4 hours at 15 ℃ to prepare a high-activity sodium silicate hydrate solution; then adding 36.24g of deionized water and 1.97g of sodium metaaluminate in sequence, stirring and mixing uniformly, and aging at 15 ℃ for 120 hours to prepare the high-activity directing agent.
2) Weighing 30.39g of coarse-pore microspherical silica gel, adding the coarse-pore microspherical silica gel into deionized water, stirring the mixture for 3.5 hours at the constant temperature of 30 ℃ to prepare high-activity hydrated silica gel, weighing 15.00g of sodium metaaluminate into the high-activity hydrated silica gel, uniformly stirring the mixture, adding 59.56g of the guiding agent, uniformly stirring the mixture, and then adding 1.5g N, N-dimethyl-N-tetradecyl aminopropyl silane quaternary ammonium salt ([ (C) into the systemnH2n+1O)3SiC3H6N(CH3)2-CxH2x+1]X, wherein n ═ 2; x is 14; x ═ Cl) to prepare a reaction gel; the total mass of the reaction gel was 179.33 g.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, crystallizing at 100 ℃ for 48 hours, and then filtering, washing and drying to obtain a NaY molecular sieve aggregate product.
The BET specific surface area of the NaY molecular sieve aggregate provided in the example is 676.51m2The silicon-aluminum ratio is 5.41, the grain size is 20-100nm, the aggregate size is 1-4 μm, and the pore volume is 0.40cm3/g。
Example 9
The embodiment provides a preparation method of a NaY molecular sieve aggregate with a nano-microstructure, which comprises the following steps:
1) the preparation method and raw material source of the directing agent are the same as those of example 1.
2) 42.54g of coarse-pore microspherical silica gel is weighed and added into 90g of deionized water, stirred for 3 hours at the constant temperature of 20 ℃ to prepare high-activity hydrated silica gel, then 21.00g of sodium metaaluminate is weighed and added into the high-activity hydrated silica gel, and after the uniform stirring, 83.38g of the guiding agent is added, and the reaction gel is prepared after the uniform stirring.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, statically crystallizing for 96 hours at 100 ℃, and then filtering, washing and drying to obtain a NaY molecular sieve aggregate product.
The specific surface area of the NaY molecular sieve aggregate provided by the embodiment is 698m2The silicon-aluminum ratio is 5.4, the grain size is 20-100nm, the aggregate size is 1-4 μm, and the pore volume is 0.43cm3/g。
Comparative example 1
The comparative example provides a method for synthesizing a NaY molecular sieve, which comprises the following steps:
this comparative example illustrates the synthesis of NaY molecular sieve by the solid phase-like method according to publication No. CN104692412A (application No. 201310656066.1), the preparation of directing agent and various sources of raw materials being the same as in example 1.
1) 57.81g of water glass is weighed and placed in a beaker, 8.81g of sodium hydroxide solid is weighed and placed in the beaker, the two are mixed and stirred uniformly, and the mixture is stirred for 2 hours at room temperature (27 ℃), so that the high-activity sodium silicate hydrate solution is prepared; and then 54.11g of deionized water and 3.12g of sodium metaaluminate are sequentially added, stirred and mixed uniformly, and aged for 36 hours at room temperature (27 ℃) to prepare the directing agent.
2) Weighing 5.00g of sodium hydroxide solid, dissolving the sodium hydroxide solid in 45g of deionized water, stirring to fully dissolve the sodium hydroxide solid to prepare an alkaline solution, weighing 42.54g of coarse-pore microspherical silica gel, adding the coarse-pore microspherical silica gel into the alkaline solution, stirring for 3 hours at a constant temperature of 20 ℃ to prepare high-activity hydrated silica gel, weighing 21.00g of sodium metaaluminate into the high-activity hydrated silica gel, uniformly stirring, adding 83.38g of the guiding agent, and uniformly stirring to prepare reaction gel, wherein the total mass of the reaction gel is 249.9 g.
3) And (3) putting the reaction gel into a stainless steel reaction kettle with a tetrachloroethylene lining, statically crystallizing for 48 hours at 100 ℃, and then filtering, washing and drying to obtain a NaY molecular sieve product.
The specific surface area of the NaY molecular sieve aggregate synthesized by the comparative example is 689.20m2The silicon-aluminum ratio is 5.30, and the grain size is 200-800 nm.
The physicochemical properties and the preparation process of the NaY molecular sieve aggregate provided by the comparative example are analyzed and shown in Table 1, the XRD spectrogram of the product is shown in figure 1, and the electron microscope map is shown in figure 3.
Claims (11)
1. A method for preparing NaY molecular sieve aggregate with a nano-microstructure comprises the following steps:
synthesizing a guiding agent;
preparing a reaction gel by using the guiding agent;
crystallizing the reaction gel to obtain a NaY molecular sieve aggregate with a nano-micro structure; wherein the content of the first and second substances,
introducing organosilicon quaternary ammonium salt in the process of synthesizing a directing agent or synthesizing the directing agent and preparing reaction gel, wherein the organosilicon quaternary ammonium salt is N, N-dimethyl-N-dodecyl aminopropyl alkoxy silane quaternary ammonium salt and/or N, N-dimethyl-N-tetradecyl aminopropyl alkoxy silane quaternary ammonium salt;
the synthesis of the directing agent comprises the following processes: according to Na2O:Al2O3:SiO2:H2O, QASCs (15-25), 1 (8-30), 250 (450) and 0-10, and uniformly mixing a silicon source, water, an alkali source, an aluminum source and an organosilicon quaternary ammonium salt, and aging to prepare a directing agent; wherein the organosilicon quaternary ammonium salt is represented by QASCs;
the preparation of the reaction gel by using the directing agent comprises the following processes:
according to Na2O:Al2O3:SiO2:H2QASCs (2-6) and (1) (5.5-10.5) and (50-150) (0-5.0) in the total feeding molar ratio, and uniformly mixing a silicon source, water, an aluminum source, a directing agent and organosilicon quaternary ammonium salt to prepare reaction gel; wherein the organosilicon quaternary ammonium salt is represented by QASCs;
in the process of preparing reaction gel, the following steps are included when uniformly mixing a silicon source, water, an aluminum source, a guiding agent and organosilicon quaternary ammonium salt:
adding a silicon source into water for pretreatment to prepare hydrated silica gel;
adding an aluminum source, a guiding agent and an organosilicon quaternary ammonium salt into the hydrated silica gel to prepare reaction gel;
the silicon source used in the process of preparing the reaction gel is a solid silicon source.
2. The method of claim 1, wherein during synthesis of the directing agent:
the silicon source comprises water glass and/or silica sol;
the aluminum source comprises one or a combination of more of sodium metaaluminate, aluminum sulfate and aluminum nitrate;
the alkali source comprises sodium hydroxide;
the water is deionized water.
3. The method of claim 1, wherein, in the preparation of the reaction gel using the directing agent:
the silicon source comprises one or a combination of more of C-type silica gel, sodium silicate and white carbon black;
the aluminum source comprises one or a combination of more of sodium metaaluminate, aluminum sulfate and aluminum nitrate;
the water is deionized water.
4. The method of claim 1, wherein the total feed molar ratio for preparing the reaction gel using the directing agent isNa2O:Al2O3:SiO2:H2O:QASiCs＝(2.5-4):1:(7-9):(85-120):(0-2.0)。
5. The method according to claim 1, wherein the temperature of the pretreatment is 0-60 ℃ and the time of the pretreatment is 2-4 h.
6. The method according to any one of claims 1 to 5, wherein, in preparing the reaction gel,
h introduced by addition of Water2The weight of O accounts for 30-80% of the total weight of the reaction gel.
7. The method of claim 6, wherein the Al introduced by the addition of a directing agent2O3Is based on the weight of Al in the reaction gel2O35-20% of the total weight.
8. The method of claim 7, wherein the SiO is introduced by addition of a quaternary ammonium salt of a silicone2In the reaction gel of SiO20.1-15% of the total weight.
9. The method of any one of claims 1-5, wherein crystallizing the reaction gel comprises:
crystallizing the reaction gel at 90-110 ℃ for 20-120 h;
and after crystallization, filtering, washing and drying.
10. A NaY molecular sieve aggregate having a nano-microstructure prepared by the method of any one of claims 1 to 9, the NaY molecular sieve aggregate having characteristics of micropores and mesopores, the overall size of the NaY molecular sieve aggregate being 1 to 5 μm, wherein the NaY molecular sieve aggregate is formed by ordered aggregation of nano-and micro-crystallites, and the size of the crystallites in the NaY molecular sieve aggregate is 5 to 100 nm.
11. The NaY molecular sieve aggregate of claim 10, wherein the pore volume of the NaY molecular sieve aggregate is 0.3-0.6cm3/g；
The BET specific surface area of the NaY molecular sieve aggregate is 650-750m2/g。
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| CN111825100B (en) * | 2019-04-18 | 2023-10-31 | 中国科学院大连化学物理研究所 | High-silicon Y molecular sieve with FAU topological structure and preparation method thereof |
| CN112723373B (en) * | 2019-10-28 | 2023-01-10 | 中国石油化工股份有限公司 | Method for synthesizing hierarchical porous NaY molecular sieve at low cost |
| CN114426286B (en) * | 2020-10-15 | 2023-08-08 | 中国石油化工股份有限公司 | Mesoporous nano Y molecular sieve and preparation method thereof |
| CN114684831B (en) * | 2020-12-31 | 2024-02-09 | 中海油天津化工研究设计院有限公司 | High silicon-aluminum ratio Y molecular sieve with high relative crystallinity and preparation method thereof |
| CN114653336A (en) * | 2022-03-24 | 2022-06-24 | 青岛华世洁环保科技有限公司 | Molecular sieve type rotating wheel and preparation method and application thereof |
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