CN110562998A - Microporous zeolite, its synthesis method and use - Google Patents

Microporous zeolite, its synthesis method and use Download PDF

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CN110562998A
CN110562998A CN201810572177.7A CN201810572177A CN110562998A CN 110562998 A CN110562998 A CN 110562998A CN 201810572177 A CN201810572177 A CN 201810572177A CN 110562998 A CN110562998 A CN 110562998A
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sio
microporous zeolite
molar ratio
microporous
alkynylene
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CN110562998B (en
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王高伟
高焕新
魏一伦
尤陈佳
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • 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
    • C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol

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Abstract

The present invention relates to a microporous zeolite, its synthesis method and application. The microporous zeolite has the formula: "(1/n) Al2O3:SiO2:(m/n)R1"schematic chemical composition shown; and the microporous zeolite framework structure has-Si-R1-a Si-unit; wherein n is 5-500; m is 0.01 to 50; r1Is C1‑20Alkylene of (C)2‑20Alkenylene of (A), C2‑20Alkynylene or phenylene of (a). What is needed isThe microporous zeolite can be used as an adsorbent or a catalyst.

Description

Microporous zeolite, its synthesis method and use
Technical Field
The present invention relates to a microporous zeolite, its synthesis method and application.
background
In industry, porous inorganic materials are widely used as catalysts and catalyst supports. The porous material has relatively high specific surface and smooth pore channel structure, so that the porous material is a good catalytic material or catalyst carrier. The porous material may generally comprise: amorphous porous materials, crystalline molecular sieves, modified layered materials, and the like.
The basic framework structure of crystalline microporous zeolites is based on rigid three-dimensional TO4(SiO4，AlO4Etc.) cell structure. In this structure TO4Sharing oxygen atoms in tetrahedral fashion, framework tetrahedrons such as AlO4Is balanced by surface cations such as Na+、H+The presence of (c) is maintained. It follows that the framework properties of zeolites can be modified by means of cation exchange. Meanwhile, a rich pore channel system with a certain pore diameter exists in the structure of the zeolite, and the pore channels are mutually staggered to form a three-dimensional network structure. Based on the above structure, zeolite has not only good catalytic activity for various organic reactions, excellent shape selectivity, but also good selectivity by modification (US6162416, US4954325, US 5362697).
Synthetic crystalline microporous zeolites are often synthesized by hydrothermal methods, and often by using specific templating or directing agents to synthesize specific zeolitic molecular sieves. These templating or directing agents are often nitrogen-containing organic compounds. However, there is a corresponding relationship between the templating or directing agent and the particular zeolitic molecular sieve. For example, for ZSM-5 having a microporous MFI structure, US3702886 found to be synthesised using Tetrapropylamine (TPA) as directing agent and US4151189 found to be C2～C9The primary amine as the directing agent can also be synthesized. Other examples are US3709979, which discloses the synthesis of ZSM-11 using tetrabutylammonium bromide as directing agent, US3832449, which discloses the synthesis of ZSM-12 using tetraethylammonium as directing agent, US4016245, which discloses the synthesis of ZSM-35 using ethylenediamine as directing agent, Zeolite (1991.Vol 11.P202), which discloses the synthesis of Zeolite Beta using tetraethylammonium hydroxide as directing agent, US4439409, which discloses the synthesis of PSH using hexamethyleneimine-3 zeolite process, US4954325 discloses a process for synthesizing MCM-22 using hexamethyleneimine, US5362697 and ZL94192390.8 disclose a process for synthesizing MCM-56 having a stable layered MWW structure by controlling crystallization time using hexamethyleneimine as a directing agent, US5236575 describes a process for synthesizing non-layered MCM-49 using hexamethyleneimine as a directing agent, and Nature (1998. vol396.353 p) discloses a process for preparing ITQ-2 having MWW structure using hexamethyleneimine as a directing agent using a layering technique. The framework structure of the above crystalline zeolite is based on inorganic silica and inorganic alumina. CN101121524A, CN101121523A, CN101172254A, US8030508 disclose that organosilicon species are doped in the microporous zeolite molecular sieve, so as to obtain organosilicon hybrid microporous zeolite. However, since it uses a silane of the formula-O-Si-R, the organic functional groups are located only at the outermost surface of the zeolite framework structure. The microporous zeolite inevitably needs to be calcined and activated during the preparation and use processes, so that the organic functional groups located on the outer surface are oxidized during the calcination and activation processes.
Disclosure of Invention
The present inventors have assiduously studied on the basis of the prior art, and have found that a microporous zeolite having a novel structure and a framework containing organic functional groups, and further found that the microporous zeolite has advantageous properties.
In particular, the present invention relates to a microporous zeolite. The microporous zeolite has the formula: "(1/n) Al2O3:SiO2:(m/n)R1"schematic chemical composition shown; and is
The microporous zeolite has-Si-R in the framework structure1-a Si-unit;
Wherein n is 5-500; m is 0.01 to 50; r1Is C1-20Alkylene of (C)2-20Alkenylene of (A), C2-20Alkynylene or phenylene of (a).
The invention also provides a synthetic method of the microporous zeolite.
The invention also provides the use of the microporous zeolite.
The invention has the beneficial effects that:
The framework structures of the microporous zeolites contemplated according to the present invention have not previously been available in the art.
According to the present invention, there is provided a microporous zeolite having a framework structure in which organic functional groups are stably present.
According to the invention, when the microporous zeolite is used as an active main body of reaction, the affinity of reactants and a microporous zeolite catalyst can be effectively improved, the microporous zeolite diffusion of organic molecules in a framework is improved, the selectivity of a target product is improved, and the activity and the stability of the catalyst are improved.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of a conventional zeolite having no organofunctional groups in the framework.
Fig. 2 is a schematic view of the as-synthesized molecular structure of the zeolite sample synthesized [ example 3 ].
Fig. 3 is a schematic view of the molecular structure of the synthesized zeolite sample after calcination [ example 3 ].
Fig. 4 is a schematic view of the as-synthesized molecular structure of the zeolite sample synthesized [ comparative example 2 ].
Fig. 5 is a schematic view of the molecular structure of the synthesized zeolite sample after calcination [ comparative example 2 ].
[ example 3 ] to haveOrganosilicons of the structure, such as bis (triethoxysilyl) ethane, are sources of organic silicon and have the formula:
as can be seen from FIGS. 2 and 3, the organic group-R is located at the outer surface1-R in the framework although it may be baked out1Can exist stably.
[ comparative example 2 ] to haveOrganosilicons of structure, e.g. dimethyl-bisThe ethoxysilane is an organic silicon source and has a structural formula as follows:
As can be seen from FIGS. 4 and 5, the silicon of dimethyldiethoxysilane is located only at the outermost surface of the backbone structure due to the two methyl groups and is very easily oxidized during firing.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
all publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
when the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, whether or not the framework structure of the microporous zeolite contains organic functional groups is determined by Si29NMR solid nuclear magnetic spectrum. Microporous zeolite containing organic functional groups, its Si29The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm29Peaks in nuclear magnetic resonance spectrum. Si of the microporous zeolite29NMR solid NMR spectroscopy was performed on a Varian 400MHz solid NMR spectrometer. Si29The resonance frequency was 79.49MHz, the chemical shift was referenced to TMS (tetramethylsilane), and the pulse latency was 5 seconds (cross-polarization) and 30 seconds, respectively.
In the description aboveHereinafter, the structure of the microporous zeolite is determined by X-ray diffraction pattern (XRD) measured by an X-ray powder diffractometer using a Cu-K α radiation source, K α 1 wavelength λ 1.5405980 aa nickel filter.
It should be expressly understood that two or more of the aspects (or embodiments) disclosed in the context of this specification can be combined with each other as desired, and that such combined aspects (e.g., methods or systems) are incorporated in and constitute a part of this original disclosure, while remaining within the scope of the present invention.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
According to one aspect of the invention, a microporous zeolite is provided. The microporous zeolite has the formula: "(1/n) Al2O3:SiO2:(m/n)R1"schematic chemical composition shown. It is known that microporous zeolites sometimes contain some amount of moisture, particularly immediately after synthesis, but it is not considered necessary to specify this amount of moisture in the present invention because the presence or absence of this moisture does not substantially affect the XRD spectrum of the microporous zeolite. In view of this, the schematic chemical composition represents, in fact, the anhydrous chemical composition of the microporous zeolite. Moreover, it is apparent that the schematic chemical composition represents the framework chemical composition of the microporous zeolite.
according to one aspect of the invention, "(1/n) Al is said exemplary chemical composition2O3:SiO2:(m/n)R1wherein n is 5 to 500 and m is 0.01 to 50.
According to one aspect of the present invention, the microporous zeolite may further generally contain organic matter (particularly organic templating agent) and water, etc. in its composition, such as those filled in its channels, immediately after synthesis. In this case, the microporous zeolite mayIn what is referred to as the "as-synthesized" microporous zeolite. Here, any organic template and water etc. present in the pores thereof can be removed by firing to obtain Al having the illustrated chemical composition, "(1/n) Al2O3:SiO2:(m/n)R1"microporous zeolite. In addition, the calcination can be performed in any manner conventionally known in the art, for example, the calcination temperature is generally 300 to 750 ℃, preferably 400 to 600 ℃, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen. For this reason, the illustrative chemical composition is sometimes referred to as a post-firing illustrative chemical composition.
According to one aspect of the invention, "(1/n) Al is said exemplary chemical composition2O3:SiO2:(m/n)R1in the formula1Is C1-20Alkylene of (C)2-20Alkenylene of (A), C2-20Alkynylene or phenylene of, preferably C1-10Alkylene of (C)2-10alkenylene of (A), C2-10Alkynylene or phenylene of (2), more preferably C1-5Alkylene of (C)2-5alkenylene of (A), C2-5Alkynylene or phenylene of (2), more preferably C1-2Alkylene of (C)2-3Alkenylene of (A), C2-3Alkynylene or phenylene of (a).
According to one aspect of the invention, the framework structure of the microporous zeolite is such that O in the Si-O-Si-unit is replaced by an organofunctional group R1Is substituted thereby having-Si-R1-Si-units.
According to one aspect of the invention, the Si of the microporous zeolite29The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm29Peaks in nuclear magnetic resonance spectrum, i.e. Si29Peaks in NMR spectra can be used to characterize whether the framework of the microporous zeolite has-Si-R1-Si-units. In particular, the microporous zeolite, whether in its as-synthesized or calcined form, has Si29The NMR solid nuclear magnetic spectra contain at least one Si between-80 ppm and +50ppm29Peaks in nuclear magnetic resonance spectrum.
According toIn one aspect of the invention, the organic functional group R1Can exist in any TO with rigidity and three dimensions4(SiO4、AlO4) Cell structure and TO4In microporous zeolites that tetrahedrally share oxygen atoms. For example, the microporous zeolite may have an MWW structure having an X-ray diffraction pattern with d-spacing maxima at 12.4 + -0.2, 11.0 + -0.3, 9.3 + -0.3, 6.8 + -0.2, 6.1 + -0.2, 5.5 + -0.2, 4.4 + -0.2, 4.0 + -0.2, and 3.4 + -0.1 angstroms. The microporous zeolite may have a BEA structure, such as zeolite beta, with d-spacing maxima at 11.34 ± 0.04, 4.13 ± 0.04, 3.96 ± 0.04, 3.32 ± 0.04, 3.02 ± 0.04, and 2.07 ± 0.04 angstroms. The microporous zeolite may have a FAU structure, such as a Y zeolite, having d-spacing maxima at 14.0 ± 0.2, 8.6 ± 0.3, 7.3 ± 0.3, 5.6 ± 0.2, 4.7 ± 0.2, 4.3 ± 0.2, 3.7 ± 0.2, 3.2 ± 0.2, 2.9 ± 0.2, and 2.8 ± 0.2 angstroms. The microporous zeolite may have an MFI structure, such as ZSM-5 zeolite, having a d-spacing maximum at 11.14 + -0.05, 9.99 + -0.05, 9.74 + -0.05, 6.36 + -0.05, 5.99 + -0.05, 5.70 + -0.05, 5.57 + -0.05, 4.98 + -0.05, 4.26 + -0.05, 3.83 + -0.05, 3.75 + -0.05, 3.72 + -0.05, 6.65 + -0.05, 3.44 + -0.05, 3.32 + -0.05, 3.05 + -0.05 Angstrom.
According to one aspect of the invention, the microporous zeolite may be synthesized by the following method. In view of the above, the present invention also relates to a method for synthesizing the microporous zeolite. The method includes the step of crystallizing a mixture (hereinafter collectively referred to as a mixture) including or formed from an inorganic silicon source, an organic silicon source, an aluminum source, a base, an organic amine template, and water to obtain the microporous zeolite.
According to one aspect of the invention, in the method of synthesizing the microporous zeolite, the source of organosilicon has the structure of formula I:
Preferably having the structure of formula II:
by using such silanes of structure I, and in particular structure II, organofunctional groups can be incorporated into the framework of the microporous zeolite, thereby ensuring that the organofunctional groups are stable during subsequent microporous zeolite processing, e.g., drying, calcining, activation.
According to one aspect of the present invention, in the organic silicon source having structure I and structure II, R1Is C1-20Alkylene of (C)2-20Alkenylene of (A), C2-20Alkynylene or phenylene of, preferably C1-10Alkylene of (C)2-10Alkenylene of (A), C2-10Alkynylene or phenylene of (2), more preferably C1-5Alkylene of (C)2-5Alkenylene of (A), C2-5Alkynylene or phenylene of (2), more preferably C1-2alkylene of (C)2-3Alkenylene of (A), C2-3Alkynylene or phenylene of (a).
According to one aspect of the present invention, in the organic silicon source having structure I and structure II, R2Each independently of the others being H, halogen OR alkoxy OR3Preferably H, Cl OR alkoxy OR3(ii) a Wherein R is3Is C1-20Alkyl of (C)2-20Alkenyl or C2-20Alkynyl of (2), preferably C1-10Alkyl of (C)2-10Alkenyl or C2-10Alkynyl of (2), more preferably C1-5Alkyl of (C)2-5Alkenyl or C2-5Alkynyl of (2), more preferably C1-2Alkyl of (C)2-3Alkenyl or C2-3Alkynyl group of (1).
According to one aspect of the present invention, the organic silicon source may be selected from the group consisting of bis (trimethoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) benzene, 1, 2-bis (trichlorosilyl) ethane, bis (dichlorosilyl) methane, bis (trichloro) silylmethane, and bis (chlorodimethylsilyl) ethane. These organic silicon sources may be used singly or in combination in a desired ratio.
In the method for synthesizing the microporous zeolite according to an aspect of the present invention, the crystallization step may be performed in any manner conventionally known in the art, such as a method of mixing the inorganic silicon source, the organic silicon source, the aluminum source, the base, the organic amine template, and water in a predetermined ratio, and hydrothermally crystallizing the obtained mixture under the crystallization conditions. In the presence of stirring as required.
According to an aspect of the present invention, in the method for synthesizing the microporous zeolite, as the inorganic silicon source, any inorganic silicon source conventionally used in the art for this purpose may be used. Examples thereof include silica sol, solid silica, silica gel, sodium silicate, diatomaceous earth and water glass. These inorganic silicon sources may be used singly or in combination of two or more in a desired ratio.
according to an aspect of the present invention, in the method for synthesizing the microporous zeolite, as the aluminum source, any aluminum source conventionally used in the art for this purpose may be used. For example, sodium aluminate, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, alumina, kaolin and montmorillonite can be mentioned. These aluminum sources may be used singly or in combination in a desired ratio.
According to an aspect of the present invention, in the synthesis method of the microporous zeolite, as the base, any base conventionally used in the art for this purpose may be used. Examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. These bases may be used singly or in combination in a desired ratio.
According to an aspect of the present invention, in the synthesis method of the microporous zeolite, as the organic amine templating agent, any organic amine templating agent conventionally used in the art for this purpose may be used. Examples thereof include ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, hexahydropyridine, butylamine, hexylamine, octylamine, quinylamine, dodecylamine, hexadecylamine and octadecylamine. These organic amine templating agents may be used singly or in combination in a desired ratio.
According to one aspect of the invention, in the synthesis method of the microporous zeolite, SiO in an inorganic silicon source is used2On the basis of SiO in the mixture2/Al2O3The molar ratio of (A) to (B) is 5-500, and the organic silicon source/SiO2In a molar ratio of 0.001 to 1, OH-/SiO2In a molar ratio of 0.01 to 5.0, H2O/SiO2The molar ratio of (A) to (B) is 5-100, and the organic amine template agent/SiO2The molar ratio of (A) to (B) is 0 to 2.0; SiO is preferred2/Al2O3The molar ratio of (A) to (B) is 10 to 250, and the organic silicon source/SiO2In a molar ratio of 0.005 to 0.5, OH-/SiO2In a molar ratio of 0.05 to 1.0, H2O/SiO2The molar ratio of (A) to (B) is 10-80, and the organic amine template agent/SiO2The molar ratio of (A) to (B) is 0 to 1.0.
According to an aspect of the present invention, in the method for synthesizing a microporous zeolite, the crystallization conditions include: the crystallization temperature is 90-250 ℃, and the crystallization time is 1-300 hours; the crystallization temperature is preferably 100-210 ℃ and the crystallization time is preferably 2-200 hours.
According to one aspect of the present invention, in the method for synthesizing the microporous zeolite, an aging step before crystallization is included; the aging conditions include: the aging temperature is 10-80 ℃, and the aging time is 2-100 hours.
According to one aspect of the present invention, in the method for synthesizing the microporous zeolite, after the crystallization is completed, the microporous zeolite may be separated from the obtained reaction mixture as a product by any separation means conventionally known, and the microporous zeolite thus obtained is also referred to as a synthetic-state form of the microporous zeolite. The separation method includes, for example, a method of filtering, washing and drying the obtained reaction mixture.
According to an aspect of the present invention, in the method for synthesizing the microporous zeolite, the filtering, washing and drying may be performed in any manner conventionally known in the art. Specifically, for example, the reaction mixture obtained may be simply filtered by suction. Examples of the washing include washing with deionized water. The drying temperature is, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure.
According to an aspect of the present invention, in the method for synthesizing the microporous zeolite, the microporous zeolite obtained by crystallization may be calcined, if necessary, to remove the organic amine template and moisture and the like that may be present, thereby obtaining a calcined microporous zeolite, also referred to as a calcined form of microporous zeolite. The calcination can be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally 300 to 800 ℃, preferably 400 to 650 ℃, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
According to one aspect of the invention, the microporous zeolite may be in any physical form, such as a powder, granules, or molded article (e.g., a bar, clover, etc.). These physical forms can be obtained in any manner conventionally known in the art and are not particularly limited.
According to one aspect of the invention, the microporous zeolite may be used in combination with other materials, thereby obtaining a microporous zeolite composition. Examples of the other materials include active materials and inactive materials. Examples of the active material include synthetic zeolite and natural zeolite, and examples of the inactive material (generally referred to as a binder) include clay, silica gel, and alumina. These other materials may be used singly or in combination in any ratio. As the amount of the other materials, those conventionally used in the art can be directly referred to, and there is no particular limitation.
According to one aspect of the invention, the microporous zeolite or the microporous zeolite composition may be used as an adsorbent, for example to separate at least one component from a mixture of components in the gas or liquid phase. Thus, at least one component may be partially or substantially completely separated from the mixture of components by contacting the mixture with the microporous zeolite or the microporous zeolite composition to selectively adsorb such component.
According to one aspect of the invention, the microporous zeolite or the microporous zeolite composition may also be used as a catalyst (or as a catalytically active component thereof) either directly or after having been subjected to the necessary treatments or conversions (such as ion exchange, etc.) conventionally performed in the art for microporous zeolites. To this end, according to one aspect of the present invention, it is possible, for example, to subject a reactant (such as a hydrocarbon) to a predetermined reaction in the presence of the catalyst, and thereby obtain a target product. For example, liquid phase alkylation of benzene with propylene to produce isopropylbenzene, liquid phase alkylation of benzene with ethylene to produce ethylbenzene, vapor phase alkylation of benzene with ethanol to produce ethylbenzene, and liquid phase alkylation of benzene with cyclohexene to produce cyclohexylbenzene, etc.
The invention is further illustrated by the following examples.
[ example 1 ]
Sodium aluminate (Al)2O342.0 wt.%)) 6.1 g was dissolved in 288.0 g of water, 1.0 g of sodium hydroxide was added to dissolve it, then 34.0 g of piperidine was added to the solution with stirring, 60.0 g of solid silica and 6.8 g of bis (triethoxysilyl) methane were added, and the mixture ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝40
NaOH/SiO2＝0.025
Bis (triethoxysilyl) methane/SiO2＝0.02
piperidine/SiO2＝0.50
H2O/SiO2＝16
After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 50 hours at the temperature of 150 ℃ under stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 42.1.
The dried sample is calcined to obtain Si29The nuclear magnetic resonance spectrum peak of the solid appears at-61.1 ppm.
The X-ray diffraction data of the dried sample are shown in Table 1.
TABLE 1
[ example 2 ]
Dissolving 3.0 g of alumina in 450 g of water, adding 16.0 g of sodium hydroxide to dissolve the alumina, then adding 34.7 g of hexamethyleneimine under the condition of stirring, adding 60 g of solid silicon oxide, and 6.8 g of bis (triethoxysilyl) methane, wherein the material ratio (molar ratio) of reactants is as follows:
SiO2/Al2O3＝30
NaOH/SiO2＝0.2
Bis (triethoxysilyl) methane/SiO2＝0.02
hexamethyleneimine/SiO2＝0.35
H2O/SiO2＝25
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 70 hours at 150 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 30.1.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-61.2 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried sample are shown in Table 2.
TABLE 2
[ example 3 ]
Sodium aluminate (Al)2O342.0 wt.%)) 3.5 g were dissolved in 540 g of water, 8.0 g of sodium hydroxide were added to dissolve it, 30 g of hexamethyleneimine were added with stirring, and a further 30 g of hexamethyleneimine were added60 g of solid silicon oxide and 7.1 g of bis (triethoxysilyl) ethane, wherein the material ratio (molar ratio) of reactants is as follows:
SiO2/Al2O3＝70
NaOH/SiO2＝0.2
Bis (triethoxysilyl) ethane/SiO2＝0.02
hexamethyleneimine/SiO2＝0.3
H2O/SiO2＝30
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 35 hours at 135 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 68.5.
the dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-60.1 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried sample are shown in Table 3.
TABLE 3
[ example 4 ]
Sodium aluminate (Al)2O342.0 wt.%) 8.0 g of the mixture was dissolved in 360 g of water, 4.0 g of sodium hydroxide was added to dissolve the mixture, 34.0 g of piperidine was added with stirring, 150 g of silica sol (silica content 40 wt.%), 7.1 g of bis (triethoxysilyl) ethane, and the material ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝30
NaOH/SiO2＝0.05
Bis (triethoxysilyl) ethane/SiO2＝0.02
piperidine/SiO2＝0.4
H2O/SiO2＝20
After the reaction mixture is stirred uniformly, the mixture is put into stainless steel for reactioncrystallizing at 150 deg.C for 55 hr in a kettle while stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 28.6.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-60.3 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried sample are shown in Table 4.
TABLE 4
[ example 5 ]
Sodium aluminate (Al)2O342.0 wt.%)) 2.4 g were dissolved in 900 g of water, 4.0 g of sodium hydroxide were added to dissolve it, 20 g of hexamethyleneimine were added with stirring, 60 g of solid silica were added, 5.4 g of bis (trimethoxysilyl) ethane, and the material ratios (molar ratios) of the reactants were:
SiO2/Al2O3＝100
NaOH/SiO2＝1.0
Bis (trimethoxysilyl) ethane/SiO2＝0.02
hexamethyleneimine/SiO2＝0.2
H2O/SiO2＝50
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 35 hours at 135 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 105.3.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-60.5 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried sample are shown in Table 5.
TABLE 5
[ example 6 ]
Sodium aluminate (Al)2O342.0 wt.%)) 16.1 g were dissolved in 540 g of water, 2.0 g of sodium hydroxide were added to dissolve it, then 30 g of hexamethyleneimine were added with stirring, 60 g of solid silica were added, 5.4 g of bis (trimethoxysilyl) ethane, and the material ratios (molar ratios) of the reactants were:
SiO2/Al2O3＝15
NaOH/SiO2＝0.05
bis (trimethoxysilyl) ethane/SiO2＝0.02
hexamethyleneimine/SiO2＝0.3
H2O/SiO2＝30
After the reaction mixture is stirred uniformly, the mixture is put into a stainless steel reaction kettle and crystallized for 38 hours at 145 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3the molar ratio was 17.5.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-60.3 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried sample are shown in Table 6.
TABLE 6
[ example 7 ]
Sodium aluminate (Al)2O342.0 wt.%) 1.6 g of the mixture was dissolved in 720 g of water, 24 g of sodium hydroxide was added to dissolve the mixture, 50 g of hexamethyleneimine was added with stirring, 60 g of solid silica was added, 4.0 g of bis (triethoxysilyl) benzene was added, and the mixture ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝150
NaOH/SiO2＝0.6
Bis (triethoxysilyl) benzene/SiO2＝0.01
hexamethyleneimine/SiO2＝0.5
H2O/SiO2＝40
After the reaction mixture is stirred uniformly, the mixture is put into a stainless steel reaction kettle and crystallized for 35 hours at 135 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3the molar ratio was 140.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-59.5 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried sample are shown in Table 7.
TABLE 7
[ COMPARATIVE EXAMPLE 1 ]
Compared to [ example 1 ], only the silane was replaced. The concrete materials are as follows: sodium aluminate (Al)2O342.0 wt.%) 6.1 g of this mixture was dissolved in 288.0 g of water, 1.0 g of sodium hydroxide was added to dissolve it, then 34.0 g of piperidine was added to the solution with stirring, 60.0 g of solid silica and 5.5g of trimethylchlorosilane were added, and the feed ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝40
NaOH/SiO2＝0.025
Trimethylchlorosilane methane/SiO2＝0.05
piperidine/SiO2＝0.50
H2O/SiO2＝16
After the reaction mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 50 hours at the temperature of 150 ℃ under stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 40.1.
Sample after drying, Si thereof29The NMR solid nuclear magnetic spectrum has a nuclear magnetic resonance spectrum peak at-16.1 ppm; the dried sample is calcined to obtain Si29The NMR spectrum of the solid does not have a nuclear magnetic resonance spectrum peak between-80 ppm and +50 ppm.
The X-ray diffraction data of the dried sample are shown in Table 8.
TABLE 8
[ example 8 ]
50 g of the powder synthesized in [ example l ] and [ comparative example 1 ] were sampled, exchanged 4 times with 1M nitric acid, filtered and dried. Then, the catalyst is fully mixed with 20 g of alumina, added with 5 weight percent of nitric acid for kneading, extruded into strips with the diameter of 1.6 multiplied by 2 mm, dried at 120 ℃, roasted at 520 ℃ for 6 hours, and prepared into the required catalyst respectively.
5.0 g of the 2 catalysts are respectively filled in a fixed bed reactor, and then mixed materials of ethylene and benzene are introduced. The reaction conditions are as follows: the weight space velocity of the ethylene is 2.0h-1The mol ratio of benzene to ethylene is 2, the reaction temperature is 220 ℃, and the reaction pressure is 3.0 MPa.
The operation was continued for 100 hours, and the reaction results are shown in Table 9.
TABLE 9
[ example 9 ]
5.0 g of the 2 catalysts are respectively filled in a fixed bed reactor, and then a mixed material of propylene and benzene is introduced. The reaction conditions are as follows: the weight space velocity of the propylene is 2.0h-1The mol ratio of benzene to propylene is 3, the reaction temperature is 155 ℃, and the reaction pressure is 3.0 MPa.
The operation was continued for 100 hours, and the reaction results are shown in Table 10.
Watch 10
[ example 10 ]
5.0 g of the 2 catalysts are respectively filled in a fixed bed reactor, and then a mixed material of the cyclic ethylene and the benzene is introduced. The reaction conditions are as follows: the weight space velocity of the cyclohexene is 0.5h-1The molar ratio of benzene to cyclohexene is 5, the reaction temperature is 170 ℃, and the reaction pressure is 3.0 MPa.
The operation was continued for 100 hours, and the reaction results are shown in Table 11.
TABLE 11
[ example 11 ]
After 3.4 g of alumina, 12.0 g of sodium hydroxide, 63 g of tetraethylammonium bromide and 450 g of water are mixed, the mixture is completely dissolved under strong stirring, 150 g of 40% silica sol and 6.8 g of bis (triethoxysilyl) methane are sequentially added, and the material ratio (molar ratio) of reactants is as follows:
SiO2/Al2O3＝30
NaOH/SiO2＝0.3
Bis (triethoxysilyl) methane/SiO2＝0.02
Tetraethyl ammonium bromide/SiO2＝0.3
H2O/SiO2＝30
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 72 hours at 195 ℃ under stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 28.5.
The dried sample is calcined to obtain Si29The nuclear magnetic resonance spectrum peak of the solid appears at-61.1 ppm.
The X-ray diffraction data of the dried sample are shown in Table 12.
TABLE 12
[ example 12 ]
Sodium aluminate (Al)2O350 wt.%), sodium hydroxide 12.0 g and tetraethyl ammonium hydroxide 58.8 g, then 660 g of water was added and stirred to dissolve the mixture, then 150 g of 40% silica sol and 6.8 g of bis (triethoxysilyl) methane were added, the mixture ratios (molar ratios) of the reactants were:
SiO2/Al2O3＝30
NaOH/SiO2＝0.3
Bis (triethoxysilyl) methane/SiO2＝0.02
Tetraethyl ammonium hydroxide/SiO2＝0.4
H2O/SiO2＝40
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 100 hours at 185 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 23.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-61.2 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried sample are shown in Table 13.
Watch 13
[ example 13 ]
Sodium aluminate (Al)2O342.0 wt.%) 6.1 g were dissolved in 480 g of water, and dissolved by adding 8.0 g of sodium hydroxide, 42 g of tetraethylammonium bromide and 29.4 g of tetraethylammonium hydroxide, and then adding 150 g of 40% silica sol and 7.1 g of bis (triethoxysilyl) ethane with stirring, wherein the material ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝40
NaOH/SiO2＝0.2
Bis (triethoxysilyl) ethane/SiO2＝0.02
Tetraethyl ammonium bromide/SiO2＝0.3
Tetraethyl ammonium hydroxide/SiO2＝0.2
H2O/SiO2＝20
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 120 hours at 170 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 35.8.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-60.1 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried samples are shown in Table 14.
TABLE 14
[ example 14 ]
1.7 g of alumina, 12.0 g of sodium hydroxide and 51.5 g of tetraethyl ammonium hydroxide are mixed, 570g of water is added and stirred to dissolve the mixture, 150 g of silica sol (the content of silica is 40 wt.%), 42 g of tetraethyl ammonium bromide and 7.1 g of bis (triethoxysilyl) ethane are added, and the material ratio (molar ratio) of reactants is as follows:
SiO2/Al2O3＝60
NaOH/SiO2＝0.3
Bis (triethoxysilyl) ethane/SiO2＝0.02
Tetraethyl ammonium bromide/SiO2＝0.2
Tetraethyl ammonium hydroxide/SiO2＝0.35
H2O/SiO2＝35
After the reaction mixture is stirred uniformly, the mixture is put into a stainless steel reaction kettle and crystallized for 65 hours at 185 ℃ under the stirring conditionThen (c) is performed. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 66.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-60.3 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried samples are shown in Table 15.
Watch 15
[ example 15 ]
8.2 g of aluminum nitrate, 12.0 g of sodium hydroxide and 66.1 g of tetraethyl ammonium hydroxide are mixed, 282 g of water is added and stirred to dissolve, 150 g of 40% silica sol and 5.4 g of bis (trimethoxysilyl) ethane are then added, and the material ratio (molar ratio) of reactants is as follows:
SiO2/Al2O3＝35
NaOH/SiO2＝0.3
bis (trimethoxysilyl) ethane/SiO2＝0.02
hexamethyleneimine/SiO2＝0.45
H2O/SiO2＝20
After the reaction mixture is stirred uniformly, the mixture is put into a stainless steel reaction kettle and crystallized for 38 hours at 145 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3the molar ratio was 33.5.
The dried sample is calcined to obtain Si29The NMR solid nuclear magnetic spectrum showed a peak at-60.3 ppm in nuclear magnetic resonance, and the X-ray diffraction data thereof are shown in Table 16.
TABLE 16
[ COMPARATIVE EXAMPLE 2 ]
Compared to [ example 11 ], only the silane was replaced. The concrete materials are as follows: the organic silicon source is dimethyl diethoxy silane, after 3.4 grams of alumina, 12.0 grams of sodium hydroxide, 63 grams of tetraethyl ammonium bromide and 450 grams of water are mixed, the mixture is completely dissolved under strong stirring, then 150 grams of 40% silica sol and 4.3 grams of dimethyl diethoxy silane are sequentially added, and the material ratio (molar ratio) of reactants is as follows:
SiO2/Al2O3＝30
NaOH/SiO2＝0.3
Dimethyldiethoxysilane/SiO2＝0.03
Tetraethyl ammonium bromide/SiO2＝0.3
H2O/SiO2＝30
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 72 hours at 195 ℃ under stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 28.9.
Sample after drying, Si thereof29The NMR solid nuclear magnetic spectrum has a nuclear magnetic resonance spectrum peak at-16.2 ppm; the dried sample is calcined to obtain Si29The NMR spectrum of the solid does not have a nuclear magnetic resonance spectrum peak between-80 ppm and +50 ppm.
The X-ray diffraction data of the dried sample are shown in Table 17.
TABLE 17
[ example 16 ]
50 g of the powder synthesized in [ example l1 ] and [ comparative example 2 ] were sampled, exchanged 4 times with 1M nitric acid, filtered and dried. Then, the catalyst is fully mixed with 20 g of alumina, added with 5 weight percent of nitric acid for kneading, extruded into strips with the diameter of 1.6 multiplied by 2 mm, dried at 120 ℃, and roasted at 520 ℃ for 6 hours to prepare the required catalyst.
1.0 g of the 2 catalysts are respectively filled in a fixed bed reactor and then introducedMixed materials of ethylene and benzene are added. The reaction conditions are as follows: the weight space velocity of the ethylene is 3.0h-1the mol ratio of benzene to ethylene is 2, the reaction temperature is 200 ℃, and the reaction pressure is 3.0 MPa.
The operation was continued for 100 hours, and the reaction results are shown in Table 18.
Watch 18
[ example 17 ]
1.0 g of the 2 catalysts are respectively filled in a fixed bed reactor, and then a mixed material of propylene and benzene is introduced. The reaction conditions are as follows: the weight space velocity of the propylene is 3.0h-1The molar ratio of benzene to propylene is 2, the reaction temperature is 155 ℃, and the reaction pressure is 3.0 MPa.
The operation was continued for 100 hours, and the reaction results are shown in Table 19.
Watch 19
[ example 18 ]
1.0 g of the 2 catalysts are respectively filled in a fixed bed reactor, and then a mixed material of the cyclic ethylene and the benzene is introduced. The reaction conditions are as follows: the weight space velocity of the cyclohexene is 1.0h-1The molar ratio of benzene to cyclohexene is 2, the reaction temperature is 160 ℃, and the reaction pressure is 3.0 MPa.
the operation was continued for 100 hours, and the reaction results are shown in Table 20.
Watch 20
[ example 19 ]
Sodium aluminate (Al)2O342.0 wt.%) 12.14 g of silica sol was dissolved in 234 g of water, 26.4 g of sodium hydroxide was added to dissolve the silica sol, 150 g of silica sol (40 wt.% silica content) and 6.8 g of bis (triethoxysilyl) methane were added, and the mixture ratio of reactants (mol:) was adjustedRatio) is:
SiO2/Al2O3＝20
NaOH/SiO2＝0.66
Bis (triethoxysilyl) methane/SiO2＝0.02
H2O/SiO2＝18
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 60 hours at the temperature of 100 ℃ under stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 42.1.
The dried sample is calcined to obtain Si29The nuclear magnetic resonance spectrum peak of the solid appears at-61.1 ppm.
The X-ray diffraction data of the dried sample are shown in Table 21.
TABLE 21
[ example 20 ]
sodium aluminate (Al)2O342.0 wt.%) 12.14 g of silica sol was dissolved in 234 g of water, 26.4 g of sodium hydroxide was added to dissolve the silica sol, 150 g of silica sol (40 wt.% of silica) and 7.1 g of bis (triethoxysilyl) ethane were added, and the material ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝20
NaOH/SiO2＝0.66
Bis (triethoxysilyl) ethane/SiO2＝0.02
H2O/SiO2＝18
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 60 hours at the temperature of 100 ℃ under stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 42.1.
The dried sample is calcined to obtain Si29Nuclear magnetic resonance of solid in-61.1 ppmA peak of the spectrum.
The X-ray diffraction data of the dried samples are shown in Table 22.
TABLE 22
[ example 21 ]
Sodium aluminate (Al)2O342.0 wt.%) 12.14 g of silica sol was dissolved in 234 g of water, 26.4 g of sodium hydroxide was added to dissolve the silica sol, 150 g of silica sol (40 wt.% of silica) and 5.4 g of bis (trimethoxysilyl) ethane were added, and the material ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝20
NaOH/SiO2＝0.66
Bis (trimethoxysilyl) ethane/SiO2＝0.02
H2O/SiO2＝18
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 60 hours at the temperature of 100 ℃ under stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 42.1.
The dried sample is calcined to obtain Si29The nuclear magnetic resonance spectrum peak of the solid appears at-60.5 ppm.
The X-ray diffraction data of the dried sample are shown in Table 23.
TABLE 23
[ example 22 ]
Sodium aluminate (Al)2O342.0 wt.%) 12.14 g of silica sol was dissolved in 234 g of water, 26.4 g of sodium hydroxide was added to dissolve the silica sol, 150 g of silica sol (40 wt.% of silica) and 4.0 g of bis (triethoxysilyl) benzene were added, and the material ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝20
NaOH/SiO2＝0.66
bis (triethoxysilyl) benzene/SiO2＝0.01
H2O/SiO2＝18
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 60 hours at the temperature of 100 ℃ under stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 42.1.
The dried sample is calcined to obtain Si29The nuclear magnetic resonance spectrum peak of the solid appears at-61.1 ppm.
The X-ray diffraction data of the dried samples are shown in Table 24.
Watch 24
[ COMPARATIVE EXAMPLE 3 ]
Compared to [ example 19 ], only silane was replaced. The concrete materials are as follows:
Sodium aluminate (Al)2O342.0 wt.%) 12.14 g of the above-mentioned mixture was dissolved in 234 g of water, 26.4 g of sodium hydroxide was added to dissolve the mixture, 150 g of silica sol (40 wt.% of silica) and 4.5 g of dimethyldiethoxysilane were added, and the mixture ratio (molar ratio) of the reactants was:
SiO2/Al2O3＝20
NaOH/SiO2＝0.66
Dimethyldiethoxysilane/SiO2＝0.03
H2O/SiO2＝18
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 60 hours at the temperature of 100 ℃ under stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 42.1.
The dried sample is calcined to obtain Si29The nuclear magnetic resonance spectrum peak of the solid appears at-15.6 ppm. The dried sample is roasted, and the Si29NMR solid nuclear magnetic spectrum of the sample has no nuclear magnetic resonance spectrum peak between-80 ppm and +50 ppm.
The X-ray diffraction data of the dried samples are shown in Table 25.
TABLE 25
[ example 23 ]
50 g of the powder synthesized in [ example l9 ] and [ comparative example 3 ] were sampled, exchanged 4 times with 1M nitric acid, filtered and dried. Then, the catalyst is fully mixed with 20 g of alumina, added with 5 weight percent of nitric acid for kneading, extruded into strips with the diameter of 1.6 multiplied by 2 mm, dried at 120 ℃, and roasted at 520 ℃ for 6 hours to prepare the required catalyst.
1.0 g of the 2 catalysts are respectively filled in a fixed bed reactor, and then a mixed material of ethylene and benzene is introduced. The reaction conditions are as follows: the weight space velocity of the ethylene is 3.0h-1. The mol ratio of benzene to ethylene is 2, the reaction temperature is 200 ℃, and the reaction pressure is 3.0 MPa.
The operation was continued for 100 hours, and the reaction results are shown in Table 26.
Watch 26
[ example 24 ]
1.0 g of the 2 catalysts are respectively filled in a fixed bed reactor, and then a mixed material of propylene and benzene is introduced. The reaction conditions are as follows: the weight space velocity of the propylene is 3.0h-1The molar ratio of benzene to propylene is 2, the reaction temperature is 155 ℃, and the reaction pressure is 3.0 MPa.
The operation was continued for 100 hours, and the reaction results are shown in Table 27.
Watch 27
[ example 25 ]
1.0 g of the 2 catalysts are respectively filled in a fixed bed reactor, and then a mixed material of ethylene and benzene is introduced. The reaction condition is that the weight space velocity of the cyclohexene is 1h-1. The molar ratio of benzene to cyclohexene is 2, the reaction temperature is 160 ℃, and the reaction pressure is 3.0 MPa.
The operation was continued for 100 hours, and the reaction results are shown in Table 28.
Watch 28
[ example 26 ]
Dissolving 4.3 g of aluminum nitrate in 540 g of water, adding 24.0 g of sodium hydroxide to dissolve the aluminum nitrate, then adding 66.5 g of tetrapropylammonium bromide under stirring, adding 60.0 g of solid silicon oxide and 6.8 g of bis (triethoxysilyl) methane, wherein the material ratio (molar ratio) of reactants is as follows:
SiO2/Al2O3＝100
NaOH/SiO2＝0.6
Bis (triethoxysilyl) methane/SiO2＝0.02
Tetrapropylammonium bromide/SiO2＝0.50
H2O/SiO2＝16
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 60 hours at 185 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 95.5.
The dried sample is calcined to obtain Si29The nuclear magnetic resonance spectrum peak of the solid appears at-61.1 ppm.
The X-ray diffraction data of the dried sample are shown in Table 29.
Watch 29
[ example 27 ]
Sodium aluminate (Al)2O342.0 wt.%)) 6.1 g were dissolved in 720 g of water, 1.6 g of sodium hydroxide were added and dissolved, then 46.4 g of hexamethylenediamine and 60 g of silica were added with stirring, 6.8 g of bis (triethoxysilyl) methane were added, and the material ratio (mole ratio) of the reactants was:
SiO2/Al2O3＝40
NaOH/SiO2＝0.4
Bis (triethoxysilyl) methane/SiO2＝0.02
Tetrapropylammonium bromide/SiO2＝0.4
H2O/SiO2＝40
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 55 hours at 150 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 41.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-61.2 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried samples are shown in Table 30.
Watch 30
[ example 28 ]
1.2 g of aluminum sulfate is dissolved in 450 g of water, 12.0 g of sodium hydroxide is added to dissolve the aluminum sulfate, 79.8 g of caged tetraethylammonium bromide is added under the condition of stirring, 150 g of silica sol (the content of silica is 40 weight percent) and 7.1 g of bis (triethoxysilyl) ethane are added, and the material ratio (molar ratio) of reactants is as follows:
SiO2/Al2O3＝300
NaOH/SiO2＝0.3
Bis (triethoxysilyl) ethane/SiO2＝0.02
Tetrapropylammonium bromide/SiO2＝0.3
H2O/SiO2＝30
After the reaction mixture was stirred uniformly, it was transferred to a stainless steel reaction vessel and crystallized at 145 ℃ for 70 hours with stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio is 290
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-60.1 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried sample are shown in Table 31.
Watch 31
[ example 29 ]
Dissolving 2.8 g of aluminum nitrate in 540 g of water, adding 20 g of sodium hydroxide to dissolve the aluminum nitrate, then adding 79.8 g of tetrapropylammonium bromide under stirring, adding 60 g of solid silicon oxide, 7.1 g of bis (triethoxysilyl) ethane, and the material ratio (mol ratio) of reactants is as follows:
SiO2/Al2O3＝150
NaOH/SiO2＝0.5
Bis (triethoxysilyl) ethane/SiO2＝0.03
Tetrapropylammonium bromide/SiO2＝0.3
H2O/SiO2＝30
After the reaction mixture is stirred uniformly, the mixture is put into a stainless steel reaction kettle and crystallized for 55 hours at the temperature of 150 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 148.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-60.3 ppm in nuclear magnetic resonance.
The X-ray diffraction data of the dried samples are shown in Table 32.
Watch 32
[ example 30 ]
Dissolving 21.3 g of aluminum nitrate in 720 g of water, adding 20 g of sodium hydroxide to dissolve the aluminum nitrate, then adding 80 g of tetrapropylammonium bromide under the condition of stirring, then adding 60 g of solid silicon oxide and 5.4 g of bis (trimethoxysilyl) ethane, wherein the material ratio (molar ratio) of reactants is as follows:
SiO2/Al2O3＝20
NaOH/SiO2＝0.5
bis (trimethoxysilyl) ethane/SiO2＝0.04
Tetrapropylammonium bromide/SiO2＝0.3
H2O/SiO2＝40
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 35 hours at 135 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 20.5.
The dried sample is calcined to obtain Si29The NMR spectrum of the solid showed a peak at-60.5 ppm in nuclear magnetic resonance, and the X-ray diffraction data thereof are shown in Table 33.
Watch 33
[ COMPARATIVE EXAMPLE 4 ]
Compared to [ example 26 ], only the silane was replaced. The concrete materials are as follows:
Dissolving 4.3 g of aluminum nitrate in 540 g of water, adding 24.0 g of sodium hydroxide to dissolve the aluminum nitrate, then adding 66.5 g of tetrapropylammonium bromide under stirring, adding 60.0 g of solid silicon oxide and 4.3 g of dimethyldiethoxysilane, wherein the material ratio (mol ratio) of the reactants is as follows:
SiO2/Al2O3＝100
NaOH/SiO2＝0.6
Dimethyldiethoxysilane/SiO2＝0.03
Tetrapropylammonium bromide/SiO2＝0.50
H2O/SiO2＝16
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 60 hours at 185 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 95.5.
The dried sample is calcined to obtain Si29The nuclear magnetic resonance spectrum peak of the solid appears at-17.1 ppm. The dried sample is roasted, and the Si29NMR solid nuclear magnetic spectrum of the sample has no nuclear magnetic resonance spectrum peak between-80 ppm and +50 ppm.
The X-ray diffraction data of the dried samples are shown in Table 34.
Watch 34
After the reaction mixture is stirred uniformly, the mixture is transferred to a stainless steel reaction kettle and crystallized for 60 hours at 185 ℃ under the condition of stirring. Taking out, filtering, washing and drying. Obtaining SiO by chemical analysis2/Al2O3The molar ratio was 98.
[ example 31 ]
50 g of the powder synthesized in [ example 26 ] and [ comparative example 4 ] were sampled, exchanged 4 times with 1M nitric acid, filtered and dried. Then, the catalyst is fully mixed with 20 g of alumina, added with 5 weight percent of nitric acid for kneading, extruded into strips with the diameter of 1.6 multiplied by 2 mm, dried at 120 ℃, and roasted at 520 ℃ for 6 hours to prepare the required catalyst.
1.0 g of the catalyst is respectively filled in a fixed bed reactor, and then mixed materials of ethanol and benzene are introduced. The reaction conditions are as follows: ethanol empty by weightThe speed is 0.8h-1The mol ratio of benzene and ethanol is 6.5, the reaction temperature is 390 ℃, and the reaction pressure is 3.0 MPa.
The operation was continued for 100 hours, and the reaction results are shown in Table 35. Watch 35

Claims (10)

1. A microporous zeolite is represented by formula: (1/n) Al2O3:SiO2:(m/n)R1"schematic chemical composition shown; and is
The microporous zeolite has-Si-R in the framework structure1-a Si-unit;
wherein n is 5-500; m is 0.01 to 50; r1Is C1-20Alkylene of (C)2-20Alkenylene of (A), C2-20Alkynylene or phenylene of, preferably C1-10Alkylene of (C)2-10Alkenylene of (A), C2-10Alkynylene or phenylene of (2), more preferably C1-5Alkylene of (C)2-5alkenylene of (A), C2-5Alkynylene or phenylene of (2), more preferably C1-2Alkylene of (C)2-3alkenylene of (A), C2-3Alkynylene or phenylene of (a).
2. The microporous zeolite of claim 1, wherein the Si of the microporous zeolite29The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm29peaks in nuclear magnetic resonance spectrum.
3. A microporous zeolite according to claim 2, characterized in that the microporous zeolite has Si in its as-synthesized or calcined form29The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm29Peaks in nuclear magnetic resonance spectrum.
4. A microporous zeolite according to claim 1, having an X-ray diffraction pattern with d-spacing maxima at 12.4 ± 0.2, 11.0 ± 0.3, 9.3 ± 0.3, 6.8 ± 0.2, 6.1 ± 0.2, 5.5 ± 0.2, 4.4 ± 0.2, 4.0 ± 0.2 and 3.4 ± 0.1 angstroms; or
D-spacing maxima at 11.34 + -0.04, 4.13 + -0.04, 3.96 + -0.04, 3.32 + -0.04, 3.02 + -0.04, and 2.07 + -0.04 angstroms; or
D-spacing maxima at 14.0 + -0.2, 8.6 + -0.3, 7.3 + -0.3, 5.6 + -0.2, 4.7 + -0.2, 4.3 + -0.2, 3.7 + -0.2, 3.2 + -0.2, 2.9 + -0.2 and 2.8 + -0.2 angstroms; or
The d-spacing maximum is at 11.14 + -0.05, 9.99 + -0.05, 9.74 + -0.05, 6.36 + -0.05, 5.99 + -0.05, 5.70 + -0.05, 5.57 + -0.05, 4.98 + -0.05, 4.26 + -0.05, 3.83 + -0.05, 3.75 + -0.05, 3.72 + -0.05, 6.65 + -0.05, 3.44 + -0.05, 3.32 + -0.05, 3.05 + -0.05.
5. A method for synthesizing a microporous zeolite, comprising the step of crystallizing a mixture containing or formed from an inorganic silicon source, an organic silicon source, an aluminum source, a base, an organic amine template and water to obtain the microporous zeolite; and optionally, a step of calcining the obtained microporous zeolite;
Wherein the organic silicon source has the structure of formula I:
Preferably having the structure of formula II:
Wherein R is1Is C1-20Alkylene of (C)2-20Alkenylene of (A), C2-20Alkynylene or phenylene of, preferably C1-10Alkylene of (C)2-10Alkenylene of (A), C2-10Alkynylene or phenylene of (2), more preferably C1-5Alkylene of (C)2-5Alkenylene of (A), C2-5alkynylene or phenylene of (2), more preferably C1-2Alkylene of (2)、C2-3Alkenylene of (A), C2-3Alkynylene or phenylene of (a);
R2Each independently of the others being H, halogen OR alkoxy OR3Preferably H, Cl OR alkoxy OR3(ii) a Wherein R is3Is C1-20Alkyl of (C)2-20Alkenyl or C2-20Alkynyl of (2), preferably C1-10Alkyl of (C)2-10Alkenyl or C2-10Alkynyl of (2), more preferably C1-5Alkyl of (C)2-5Alkenyl or C2-5Alkynyl of (2), more preferably C1-2Alkyl of (C)2-3Alkenyl or C2-3alkynyl group of (1).
6. A process for the synthesis of a microporous zeolite according to claim 5,
The inorganic silicon source is at least one selected from the group consisting of silica sol, solid silica, silica gel, sodium silicate, diatomaceous earth and water glass;
the aluminum source is at least one selected from the group consisting of sodium aluminate, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, alumina, kaolin, and montmorillonite;
The alkali is at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide;
The organic amine template is at least one selected from the group consisting of ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, piperidine, butylamine, hexylamine, octylamine, quinamine, dodecylamine, hexadecylamine and octadecylamine;
By SiO in inorganic silicon source2On the basis of SiO in the mixture2/Al2O3the molar ratio of (A) to (B) is 5-500, and the organic silicon source/SiO2In a molar ratio of 0.001 to 1, OH-/SiO2In a molar ratio of 0.01 to 5.0, H2O/SiO2The molar ratio of (A) to (B) is 5-100, and the organic amine template agent/SiO2The molar ratio of (A) to (B) is 0 to 2.0; SiO is preferred2/Al2O3The molar ratio of (A) to (B) is 10 to 250, and the organic silicon source/SiO2In a molar ratio of 0.005 to 0.5, OH-/SiO2In a molar ratio of 0.05 to 1.0, H2O/SiO2The molar ratio of (A) to (B) is 10-80, and the organic amine template agent/SiO2The molar ratio of (A) to (B) is 0 to 1.0.
7. A synthesis process for a microporous zeolite according to claim 5, wherein the crystallization conditions include: the crystallization temperature is 90-250 ℃, and the crystallization time is 1-300 hours; the crystallization temperature is preferably 100-210 ℃ and the crystallization time is preferably 2-200 hours.
8. A process for the synthesis of a microporous zeolite according to claim 5, wherein said process comprises an aging step prior to crystallization; the aging conditions include: the aging temperature is 10-80 ℃, and the aging time is 2-100 hours.
9. A microporous zeolite composition comprising the microporous zeolite according to any one of claims 1 to 4 or the microporous zeolite synthesized by the method for synthesizing the microporous zeolite according to any one of claims 5 to 8, and a binder.
10. Use of a microporous zeolite according to any one of claims 1 to 4, a microporous zeolite synthesized according to the method for synthesizing a microporous zeolite according to any one of claims 5 to 8, or a microporous zeolite composition according to claim 9 as an adsorbent or catalyst.
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