CN114477203B - Porous molecular sieve and synthesis method thereof - Google Patents
Porous molecular sieve and synthesis method thereof Download PDFInfo
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- CN114477203B CN114477203B CN202011148633.9A CN202011148633A CN114477203B CN 114477203 B CN114477203 B CN 114477203B CN 202011148633 A CN202011148633 A CN 202011148633A CN 114477203 B CN114477203 B CN 114477203B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 57
- 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 57
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 45
- 239000013078 crystal Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- 238000002441 X-ray diffraction Methods 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- -1 silane compound Chemical class 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 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 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 241000625836 Ochrolechia Species 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical class CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B01J35/60—
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- 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
Abstract
The invention discloses a porous molecular sieve and a synthesis method thereof. The porous molecular sieve is spherical crystal with the diameter of 500 nm-10 mu m, al 2 O 3 /SiO 2 The weight ratio is 0-0.5. The porous molecular sieve has good hydrophobicity. The novel hydrophobic porous molecular sieve material is directly synthesized in one step, an organic template agent is not needed, the preparation method is simple, and the problem of poor hydrophobicity of the porous material is well solved.
Description
Technical Field
The invention relates to the field of molecular sieves and preparation, in particular to a novel porous molecular sieve and a synthesis method thereof.
Background
Molecular sieves with unique pore structure, strong acidity and redox properties are one of the most important catalytic materials in the industry at present, and have been used in more and more catalytic reactions. At present, most zeolite molecular sieve synthesis adopts a traditional hydrothermal synthesis method. The molecular sieve obtained by the method contains a large amount of silicon hydroxyl groups, so that the hydrophobicity is greatly reduced, and the application of the molecular sieve is limited.
In addition to being hydrophobic, the morphology of the molecular sieve also plays a significant role in the reaction. Since reactant molecules react in the molecular sieve pores, and the diffusion rate is precisely related to the morphology and the particle size of the molecular sieve, the crystal morphology of the molecular sieve can significantly affect the performance and practical application of the molecular sieve. It has been demonstrated that the morphology of molecular sieves has an effect on the catalytic process, such as on the product distribution of the cracking reaction and the conversion of methanol to hydrocarbons, and on the stability of the catalyst (Xu Feng, dong Mei, huang Lizhi, etc.. ZSM-5 molecular sieves have a controlled synthesis of particle size and their catalytic action in methanol conversion [ J ]]Fuel chemistry journal 2012 (5): 576-582.). In addition, it has been found that the morphology of the molecular sieve affects the selectivity of the reaction, such as in toluene disproportionation reactions, the spherulitic molecular sieve favors the formation of meta-isomers, whereas the use of a columnar molecular sieve primarily forms para-isomers (BRANDENBERGER S,O，WOKAUN A，et al.The role of />acidity in the selective catalytic reduction of NO with ammonia over Fe-ZSM-5[J].J.Catal.，2009，268(2)：297-306.)。
in addition, the hydrophobic molecular sieve material is mainly obtained by a post-treatment method, and the method not only ensures low crystallinity, but also increases production procedures, reduces molecular sieve yield and increases production cost. Compared with the post-treatment method, the one-step synthesis method can avoid the complicated post-treatment process, save a great deal of manpower and material resources, reduce the pollution to the environment, and simultaneously has better catalysis and adsorption effects due to uniform chemical distribution. Therefore, the development of a novel molecular sieve hydrophobic material which is simple in preparation process and environment-friendly has important significance.
Disclosure of Invention
The invention provides a porous molecular sieve and a synthesis method thereof, wherein the porous molecular sieve has good hydrophobicity. The novel hydrophobic porous molecular sieve material is directly synthesized in one step, an organic template agent is not needed, the preparation method is simple, and the problem of poor hydrophobicity of the porous material is well solved.
The first aspect of the present invention provides a porous molecular sieve having X-ray diffraction peaks as shown in the following table:
wherein, (a) = ±0.5°, (b) varies with 2θ.
Further, the porous molecular sieve is spherical crystals with a diameter of 500nm to 10 μm, preferably 1 μm to 5 μm, al 2 O 3 /SiO 2 The weight ratio is 0-0.5.
The second aspect of the present invention provides a method for preparing a porous molecular sieve, comprising the steps of:
a) Mixing an alkali source R1, a silicon source, an optional organic solvent R2, optional water and an optional aluminum source to obtain a mixture, wherein the aluminum source is prepared by the following steps of Al 2 O 3 Gauge, silicon source per SiO 2 The weight ratio of the mixture is as follows: R1/SiO 2 ＝0.2～2.5；Al 2 O 3 /SiO 2 ＝0～2.5；H 2 O/SiO 2 ＝0～300；R2/SiO 2 =0 to 300, and water and organic solvent R2 are not simultaneously 0;
b) And (3) carrying out crystallization reaction on the mixture to obtain the porous molecular sieve.
Further, the alkali source R1 is at least one selected from alkaline compounds such as sodium hydroxide, potassium hydroxide, ammonia water, and the like. The organic solvent R2 is at least one selected from ethanol, acetone, n-hexane, toluene and other organic solvents. The aluminum source is selected from at least one of aluminum-containing compounds such as aluminum isopropoxide, pseudo-boehmite, aluminum oxide, aluminum nitrate, aluminum chloride, aluminum sulfate, sodium aluminate and the like. The silicon source is at least one selected from the group consisting of silane compounds, siloxane compounds, and silicon compounds containing alkyl or alkoxy branches such as silicone oil polymers, preferably at least one selected from the group consisting of hexamethyl siloxane, silicone oil polymers, methoxy siloxane compounds, and ethoxy silane compounds.
Further, the alkali source R1, the silicon source, the optional organic solvent R2, the optional water and the optional aluminum source are stirred for 3 to 6 hours at the temperature of-20 to 100 ℃ to obtain a mixture.
Further, the mixture is preferably left to stand and age for 12-24 hours before the crystallization reaction.
Further, the mixture preferably comprises the following components in percentage by weight: R1/SiO 2 ＝0.01～2.5；Al 2 O 3 /SiO 2 ＝0.005～2；H 2 O/SiO 2 ＝0.001～300；R2/SiO 2 ＝0.01～290。
Further, the crystallization reaction conditions are as follows: crystallization is carried out at 70-200 ℃ for 0.1-4.5 days, preferably at 90-200 ℃ for 0.2-4.5 days.
Further, after the crystallization reaction is finished, conventional washing, drying and optional roasting are carried out to obtain the porous molecular sieve. The drying conditions are as follows: drying at 50-150 deg.c for 8-15 hr; the roasting conditions are as follows: roasting for 3-8 h at 150-550 ℃.
In a third aspect, the present invention provides the use of the porous molecular sieve as an adsorbent or catalyst.
Compared with the prior art, the invention has the following advantages:
the novel porous molecular sieve has spherical morphology, is a molecular sieve material with better hydrophobicity which is directly synthesized by a one-step method, and can avoid a complicated post-treatment process and save a large amount of manpower and material resources by the preparation method; in addition, the use of an organic template agent is avoided in the synthesis process, so that the pollution to the environment is reduced. In addition, the preparation process is simple, the specific volume of silicon aluminum is easy to regulate and control, and the amplification is easy.
Drawings
FIG. 1 is an XRD spectrum of the novel porous molecular sieve obtained [ example 1 ];
FIG. 2 is an SEM image of the novel porous molecular sieve obtained in example 1;
FIG. 3 is an infrared spectrum of the novel porous molecular sieve obtained [ example 1 ].
Detailed Description
In order to facilitate understanding of the present invention, the present invention is exemplified by the following examples. It will be apparent to those skilled in the art that the examples are merely to aid in the understanding of the present invention and should not be construed as a specific limitation thereof.
In the context of this specification, vw, w, m, s, vs in the XRD data of the molecular sieve represents the diffraction peak intensity, vw is very weak, w is weak, m is medium, s is strong, vs is very strong, as is well known to those skilled in the art. Generally, vw is less than 5%; w is 5% -20%; m is 20% -40%; s is 40% -70%; vs is greater than 70%.
In the context of the present specification, the structure of a molecular sieve is determined by an X-ray diffraction pattern (XRD) determined by an X-ray powder diffractometer using a Cu-K alpha radiation source, K alpha 1 wavelengthA nickel filter.
In the invention, an X' Pert PRO X-ray powder diffraction (XRD) instrument of the Panac company of Netherlands is adopted, the working voltage is 40kV, the current is 40mA, and the scanning range is 5-40 degrees. The morphology of the product was photographed by a field emission scanning electron microscope (Fe-SEM) model S-4800 from HITACHI corporation of Japan. The infrared spectrum was obtained by using Nicolet6700 from Siemens technology (China) with a resolution of 4cm-1 and a scanning frequency of 32 times.
It is specifically noted that two or more aspects (or embodiments) disclosed in the context of this specification may be arbitrarily combined with each other, and the resulting solution (such as a method or system) is part of the original disclosure of this specification, while also falling within the scope of the invention.
Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.
[ example 1 ]
Uniformly mixing 0.3 g of aluminum hydroxide, 0.3 g of sodium hydroxide, 46 g of water and 10 g of acetone, adding 11 g of tetramethoxysilane, stirring the prepared solution for 4 hours at room temperature, standing and aging for 12 hours; placing the aged solution into a crystallization kettle with a polytetrafluoroethylene lining, and crystallizing for 2d at 100 ℃;
wherein the weight ratio of each component in the mixture is as follows: R1/SiO 2 ＝0.07，Al 2 O 3 /SiO 2 ＝0.08；H 2 O/SiO 2 ＝11；R2/SiO 2 =1.8, wherein R1, R2 represent sodium hydroxide and acetone, respectively. Washing and centrifuging the obtained product, drying at 110deg.C for 12 hr to obtain novel porous molecular sieve product which is spherical crystal with diameter of about 2 μm, al 2 O 3 /SiO 2 The weight ratio is 0.67; the XRD pattern is shown in figure 1, the SEM pattern is shown in figure 2, and the infrared spectrum is shown in figure 3.
XRD spectrum data of the final product are shown in table 1:
TABLE 1
[ example 2 ]
Uniformly mixing 6 g of sodium hydroxide, 46 g of water and 10 g of toluene, adding 11 g of tetramethoxysilane, stirring the prepared solution for 4 hours at room temperature, standing and aging for 12 hours; placing the aged solution into a crystallization kettle with a polytetrafluoroethylene lining, and crystallizing for 2d at 150 ℃;
the weight ratio of each component is as follows: R1/SiO 2 ＝1.4，Al 2 O 3 /SiO 2 ＝0；H 2 O/SiO 2 ＝11；R2/SiO 2 =3.5, wherein R1, R2 represent sodium hydroxide and toluene, respectively. The obtained product is washed, centrifuged and dried for 12 hours at 110 ℃ to obtain a novel porous molecular sieve product, and the novel porous molecular sieve is spherical crystal with the diameter of about 2 mu m. The XRD pattern is similar to FIG. 1, the SEM pattern is similar to FIG. 2, and the IR pattern is similar to FIG. 3.XRD spectrum data of the final product are shown in table 2:
TABLE 2
[ example 3 ]
Uniformly mixing 0.6 g of aluminum hydroxide, 3 g of sodium hydroxide and 46 g of water, adding 15 g of ethoxysilane, stirring the prepared solution for 4 hours at room temperature, standing and aging for 12 hours; placing the aged solution into a crystallization kettle with a polytetrafluoroethylene lining, and crystallizing for 4d at 150 ℃;
the weight ratio of each component is as follows: R1/SiO 2 ＝0.7，Al 2 O 3 /SiO 2 ＝0.16；H 2 O/SiO 2 ＝11；R2/SiO 2 =0, wherein R1, R2 represent sodium hydroxide and toluene, respectively.
Washing, centrifuging, drying at 110deg.C for 12 hr to obtain novel porous molecular sieve product which is spherical crystal with diameter of about 3.5 μm, al 2 O 3 /SiO 2 The weight ratio is 0.2. The XRD pattern is similar to FIG. 1, the SEM pattern is similar to FIG. 2, and the IR pattern is similar to FIG. 3.XRD spectrum data of the final product are shown in table 3:
TABLE 3 Table 3
[ example 4 ]
Uniformly mixing 0.3 g of aluminum hydroxide, 3 g of sodium hydroxide and 10 g of toluene, adding 11 g of methoxysilane, stirring the prepared solution for 4 hours at room temperature, standing and aging for 12 hours; placing the aged solution into a crystallization kettle with a polytetrafluoroethylene lining, and crystallizing for 3d at 150 ℃;
the weight ratio of each component is as follows: R1/SiO 2 ＝0.7，Al 2 O 3 /SiO 2 ＝0.08；H 2 O/SiO 2 ＝0；R2/SiO 2 =3.5, wherein R1, R2 represent sodium hydroxide and toluene, respectively.
Washing, centrifuging, drying at 110deg.C for 12 hr to obtain novel porous molecular sieve product which is spherical crystal with diameter of about 2.2 μm, al 2 O 3 /SiO 2 The weight ratio was 0.77. The XRD pattern is shown in figure 1, the XRD pattern is similar to figure 1, the SEM pattern is similar to figure 2, and the infrared spectrum is similar to figure 3.XRD spectrum data of the final product are shown in table 4:
TABLE 4 Table 4
[ example 5 ]
Uniformly mixing 1.2 g of aluminum hydroxide, 3 g of sodium hydroxide and 10 g of toluene, adding 20 g of organic silicone oil polymer, stirring the prepared solution for 4 hours at room temperature, standing and aging for 12 hours; placing the aged solution into a crystallization kettle with a polytetrafluoroethylene lining, and crystallizing for 2d at 150 ℃;
the weight ratio of each component is as follows: R1/SiO 2 ＝0.7，Al 2 O 3 /SiO 2 ＝0.33；H 2 O/SiO 2 ＝11；R2/SiO 2 =3.5, wherein R1, R2 represent sodium hydroxide and toluene, respectively.
Washing, centrifuging, drying at 110deg.C for 12 hr to obtain novel porous molecular sieve product which is spherical crystal with diameter of about 1.8 μm, Al 2 O 3 /SiO 2 The weight ratio was 0.33. The XRD pattern is similar to FIG. 1, the SEM pattern is similar to FIG. 2, and the IR pattern is similar to FIG. 3.XRD spectrum data of the final product are shown in table 5:
TABLE 5
Claims (13)
1. A porous molecular sieve characterized by: the porous molecular sieve has X-ray diffraction peaks as shown in the following table:
Wherein, (a) = ±0.5°, (b) varies with 2θ;
w, m, s, vs the intensity of diffraction peak, w is 5% -20%; m is 20% -40%; s is 40% -70%; vs is greater than 70%.
2. The porous molecular sieve according to claim 1, wherein: the porous molecular sieve is spherical crystal with the diameter of 500 nm-10 mu m, al 2 O 3 /SiO 2 The weight ratio is 0-0.5.
3. The porous molecular sieve according to claim 1, wherein: the diameter of the porous molecular sieve is 1-5 mu m.
4. A process for preparing a porous molecular sieve according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
a) Mixing an alkali source R1, a silicon source, an optional organic solvent R2, optional water and an optional aluminum source to obtain a mixture, wherein the aluminum source is prepared by the following steps of Al 2 O 3 Gauge, silicon source per SiO 2 The weight ratio of the mixture is as follows: R1/SiO 2 =0.2～2.5；Al 2 O 3 /SiO 2 =0～2.5；H 2 O/SiO 2 =0～300；R2/ SiO 2 =0 to 300, and water and organic solvent R2 are not simultaneously 0;
b) And (3) carrying out crystallization reaction on the mixture to obtain the porous molecular sieve.
5. The method of claim 4, wherein: the alkali source R1 is at least one selected from sodium hydroxide, potassium hydroxide and ammonia water; the organic solvent R2 is at least one selected from ethanol, acetone, n-hexane and toluene; the aluminum source is at least one selected from aluminum isopropoxide, pseudo-boehmite, aluminum oxide, aluminum nitrate, aluminum chloride, aluminum sulfate and sodium aluminate; the silicon source is selected from at least one of silane compound, siloxane compound and organic silicone oil polymer.
6. The method according to claim 5, wherein: the silicon source is at least one selected from hexamethyl siloxane, organic silicon oil polymer, methoxy siloxane compound and ethoxy silane compound.
7. The method of claim 4, wherein: the alkali source R1, the silicon source, the optional organic solvent R2, the optional water and the optional aluminum source are stirred for 3 to 6 hours at the temperature of-20 ℃ to 100 ℃ to obtain a mixture.
8. The method of claim 4, wherein: the mixture is firstly kept stand and aged for 12-24 hours before crystallization reaction.
9. The method of claim 4, wherein: the weight ratio of the mixture is as follows: R1/SiO 2 =0.01～2.5；Al 2 O 3 /SiO 2 =0.005～2；H 2 O/SiO 2 =0.001～300；R2/ SiO 2 = 0.01～290。
10. The method of claim 4, wherein: the crystallization reaction conditions are as follows: crystallizing at 70-200 deg.c for 0.1-4.5 days.
11. The method of claim 10, wherein: the crystallization reaction conditions are as follows: crystallizing at 90-200 deg.c for 0.2-4.5 days.
12. The method of claim 4, wherein: and after the crystallization reaction is finished, washing, drying and optionally roasting are carried out to obtain the porous molecular sieve.
13. Use of a porous molecular sieve according to any one of claims 1 to 3 or prepared according to the method of any one of claims 4 to 12 as an adsorbent or catalyst.
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