CN108435245B - Small-grain-grade-pore SAPO-34@ kaolin microsphere catalyst and preparation and application thereof - Google Patents

Small-grain-grade-pore SAPO-34@ kaolin microsphere catalyst and preparation and application thereof Download PDF

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CN108435245B
CN108435245B CN201810357940.4A CN201810357940A CN108435245B CN 108435245 B CN108435245 B CN 108435245B CN 201810357940 A CN201810357940 A CN 201810357940A CN 108435245 B CN108435245 B CN 108435245B
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kaolin
sapo
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CN108435245A (en
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刘海燕
张丽娜
鲍晓军
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China University of Petroleum Beijing
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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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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  • Chemical Kinetics & Catalysis (AREA)
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention provides a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: preparing kaolin microspheres, and roasting to obtain activated kaolin microspheres; mixing the active kaolin microspheres, water, a phosphorus source, a microporous template and a mesoporous template to prepare reactant gel; crystallizing the reactant gel, and performing centrifugal separation to obtain a small-grain-grade-hole SAPO-34@ kaolin microsphere composite material; and roasting the small-grain-grade-hole SAPO-34@ kaolin microsphere composite material to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere catalyst. The SAPO-34@ kaolin microsphere catalyst has the advantages that the SAPO-34 molecular sieve content is high, the crystal grain is small, and the SAPO-34@ kaolin microsphere catalyst is provided with hierarchical pores; compared with the product obtained without adding the mesoporous template agent, the product has higher yield of in-situ products.

Description

Small-grain-grade-pore SAPO-34@ kaolin microsphere catalyst and preparation and application thereof
Technical Field
The invention relates to the technical field of chemical industry, in particular to a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, and preparation and application thereof.
Background
Ethylene and propylene are the most important basic organic chemical raw materials in the chemical industry, and play a significant role in the field of modern petrochemical industry. In recent years, as the amount of stored petroleum is gradually reduced and the supply of petroleum is gradually reduced, a process route for producing ethylene and propylene from naphtha is under severe examination, and therefore, a process route for preparing low-carbon olefins such as ethylene and propylene by replacing the petroleum route is inevitably required. Through years of research of researchers, a route for preparing low-carbon olefin from coal or natural gas serving as a raw material through methanol or dimethyl ether is a process route which is hopeful to replace a naphtha route. The catalyst for preparing olefin (MTO) from methanol in industry at present is a catalyst taking SAPO-34 as an active component, and the synthesis process is briefly described as follows: synthesizing microporous SAPO-34 molecular sieve raw powder by using a chemical reagent, mixing the microporous SAPO-34 molecular sieve raw powder with a substrate (generally kaolin), a binder, a pore-forming agent, water and the like, stirring, pulping, and spray-drying to obtain pellets of about 80-100 mu m, namely the MTO catalyst. This process is known as a "semi-synthesis" process and the MTO catalyst prepared by this "semi-synthesis" process suffers from two disadvantages: firstly, the synthesized SAPO-34 molecular sieve is usually a microporous molecular sieve, and the pore size of the molecular sieve is small, so that the SAPO-34 molecular sieve is not beneficial to the diffusion of reactants and products and is easy to coke and inactivate; secondly, the active components of the catalyst prepared by semi-synthesis are not uniformly distributed, and the pore channels are blocked by the binder and are not communicated with the pore channels of the catalyst, so that the catalyst is easy to deactivate.
Research shows that in the MTO reaction, the grain size of the SAPO-34 molecular sieve is reduced, which is beneficial to the diffusion of reactants and products; on the other hand, mesopores are introduced into the microporous molecular sieve to synthesize the SAPO-34 molecular sieve with a hierarchical pore structure, and the diffusion of reactants and products can also be improved, so that the service life of the catalyst and the selectivity of diene (ethylene and propylene) are improved, the reaction depth can be effectively inhibited, the carbon deposition rate is reduced, and the carbon capacity is improved; thirdly, the in-situ crystallization method is adopted to grow the molecular sieve crystal in situ on the substrate, thereby avoiding the problems of uneven distribution of active components and pore channel blockage caused by the preparation of the catalyst by a semi-synthesis method.
There have been many studies on small-grained and graded-pore SAPO-34 molecular sieves, such as: liu hong star applied a series of patents on how to synthesize small-grained SAPO-34 molecular sieves: CN104445266A, CN103420391A and CN 102464338A. The method reported by CN104445266A comprises the steps of firstly carrying out initial crystallization on SAPO-34 for 1-10h to obtain defective SAPO-34 crystal seeds, then adding the defective SAPO-34 crystal seeds into initial crystallization liquid of SAPO-34, carrying out hydrothermal treatment at the temperature of 140-170 ℃ for 0.1-4h to dissolve the defective crystal seeds, and then continuing heating and crystallizing to obtain the SAPO-34 molecular sieve with small crystal grains; CN103420391A reports a method for preparing small-grain SAPO-34 by fractional crystallization, specifically comprising the steps of crystallizing at 250 ℃ for 1-20h under 180-; the procedure of CN102464338A was similar to that of CN104445266A except that an HF solution was added to the starting material.
Few reports have been made on the preparation of hierarchical pore SAPO-34. CN 106608632A introduces a preparation method of SAPO-34 molecular sieve with a hierarchical pore structure, which mainly obtains hierarchical pores by adding a nano carbon black hard template agent into synthetic gel; CN 104525250 a and CN 105858684 a report methods for preparing hierarchical pore SAPO-34 molecular sieves by introducing broken seed crystals and seed crystals of nanoplatelets; patent CN 104973608A reports preparation of multi-stage pore SAPO-34 molecular sieve by adding polyethylene glycol into synthetic gel; CN 107285342A reports a method for preparing a hierarchical pore SAPO-34 molecular sieve by aftertreatment, namely, the SAPO-34 molecular sieve and solid acid are crushed and mixed uniformly and react for a certain time at the temperature of 20-120 ℃ to obtain the hierarchical pore SAPO-34 molecular sieve; the small-grain or multi-stage pore SAPO-34 molecular sieve obtained by the series of preparation methods has good reaction performance, however, the reported synthesis methods are all non-in-situ synthesis, and the defects of a semi-synthetic catalyst exist when the SAPO-34 molecular sieve is used.
In summary, the existing literature reports that the small-grain or multi-stage pore SAPO-34 molecular sieve is prepared mainly by an ex-situ method by changing the synthesis process and synthesis conditions, and the obtained molecular sieve needs to be prepared into the MTO catalyst by a semisynthetic method, so that the in-situ synthesis method has important significance in developing the in-situ synthesis small-grain and multi-stage pore SAPO-34 molecular sieve catalytic material and catalyst with good diffusion performance and high catalytic performance.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst. The method is realized by adopting kaolin microspheres as raw materials to provide all silica-alumina sources synthesized by the SAPO-34 molecular sieve, taking the kaolin microspheres as a matrix for the growth of the molecular sieve, supplementing a phosphorus source, adding a specific mesoporous template agent in the synthesis process, and crystallizing in situ.
Another object of the present invention is to provide a high yield SAPO-34@ kaolin microsphere catalyst.
The invention also aims to provide a method for preparing olefin from methanol.
In order to achieve the purpose, the invention provides a preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, wherein the method comprises the following steps:
(1) preparing kaolin microspheres, and roasting to obtain activated kaolin microspheres;
(2) mixing the activated kaolin microspheres obtained in the step (1), water, a phosphorus source, a micropore template and a mesoporous template to prepare a reactant gel, wherein the molar ratio of the components meets the following conditions:
(0.20-0.30)SiO2:(0.58-1.85)Al2O3:(1.5-3.1)P2O5:(3.5-6.5)R1:(0.1-0.7)(R2+R3):(100-300)H2o, wherein R1 is a microporous template, R2 and R3 are mesoporous templates, and a silicon source and an aluminum source are both from kaolin microspheres;
(3) crystallizing the reactant gel obtained in the step (2), and then performing centrifugal separation to obtain a small-grain-grade-hole SAPO-34@ kaolin microsphere composite material;
(4) and (4) roasting the composite material obtained in the step (3) to obtain the small-grain-grade-pore SAPO-34@ kaolin microsphere catalyst.
The preparation method provided by the invention utilizes silicon and aluminum species in kaolin as one of raw materials for synthesizing the SAPO-34 molecular sieve, supplements a phosphorus source, and induces and synthesizes the SAPO-34@ kaolin microsphere catalyst with small-grain grade pores by introducing a specific template agent. The method of the invention uses the silicon-aluminum component in the kaolin as the raw material for synthesizing the SAPO-34 molecular sieve, can reduce the synthesis cost to a great extent, and the synthesized SAPO-34 has the characteristic structure of small crystal grains and step holes, has high yield and is beneficial to improving the MTO reaction performance.
In the present invention, the silicon and aluminum species (i.e., silicon source and aluminum source) provided by kaolin are silicon and aluminum species which can be extracted by hydrochloric acid or sodium hydroxide solution after the kaolin microspheres are roasted, and enter reactant gel to be used as silicon and aluminum species for molecular sieve synthesis.
In the preparation method of the present invention, the kaolin microspheres in step (1) may be prepared according to a conventional method in the prior art, and in step (1), the kaolin microspheres may be prepared by mixing kaolin with water and a binder and then spray-drying the mixture. Specifically, the kaolin may be pulverized, sieved, and then mixed with water and a binder.
In the production method of the present invention, in the step (1), the mass ratio of kaolin to the binder is preferably 2.5 to 3: 1.
In the preparation method of the present invention, in step (1), the binder is preferably a mixture of one or more of water glass, aluminum sol, and silica sol.
In the preparation method of the present invention, preferably, in the step (1), the temperature of the calcination is 700-900 ℃, more preferably 800 ℃; the roasting time is 1-6h, and more preferably 3-4 h.
In the preparation method of the present invention, in step (1), the kaolin microspheres may be prepared according to the conventional kaolin microsphere size in the prior art, and preferably, the particle size of the kaolin microspheres is 80-110 μm.
In the preparation method of the present invention, the order of addition in step (2) may be: water-phosphoric acid-microporous template agent-kaolin microsphere-mesoporous template agent R2-mesoporous template agent R3. When the mesoporous template is added, the mesoporous template R2 is added firstly, and then the mesoporous template R3 is added. The mesoporous templating agent R3 needs to be thoroughly dissolved with a certain amount of deionized water before addition.
In the production method of the present invention, preferably, the step (2) comprises: mixing a mesoporous template R3 with part of water, stirring overnight to fully dissolve the mesoporous template R3 to obtain a solution A; uniformly mixing a phosphorus source with part of water, adding a microporous template agent R1, uniformly mixing, adding the activated kaolin microspheres obtained in the step (1), then adding a mesoporous template agent R2, stirring to fully mix, and adding the solution A.
In the production method of the present invention, preferably, in the step (2), the molar ratio of each component preferably satisfies the following condition: (0.2-0.27) SiO2:(1-1.25)Al2O3:(1.7-2.6)P2O5:(3.9-5.9)R1:(0.13-0.61)(R2+R3):(114-300)H2O。
In the preparation method of the present invention, preferably, in the step (2), the mesoporous templating agent R2 is added and then subjected to an aging treatment, and the temperature of the aging treatment may be controlled to 40 to 90 ℃, preferably 70 ℃.
In the preparation method of the present invention, preferably, in the step (2), the solution a containing the mesoporous template R3 is added after adding the mesoporous template R2 and aging for 0-5 h; preferably after 3.5h of aging treatment.
In the preparation method of the present invention, preferably, the microporous template is triethylamine.
In the production method of the present invention, preferably, the phosphorus source is orthophosphoric acid.
In the preparation method of the present invention, preferably, the mesoporous template R2 is selected from one of cationic surfactants, such as cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, and dodecyl trimethyl ammonium bromide.
In the preparation method of the present invention, preferably, the mesoporous templating agent R3 is selected from one of organosilanes dimethylhexadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride and dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride.
In the preparation method of the present invention, preferably, in the step (3), the temperature of the crystallization treatment is 180-220 ℃, preferably 200 ℃; the time for crystallization treatment is 24-72h, preferably 48 h.
In the preparation method of the invention, preferably, after crystallization, the step (3) is performed with standing sedimentation, centrifugal separation, washing, drying and other steps to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere composite material. Standing for 2-15 min. The drying temperature can be controlled to be 100-120 ℃, the drying is carried out in the air atmosphere, and the drying time can be 4-12 h.
In the preparation method of the present invention, preferably, in the step (4), the calcination temperature is 500-650 ℃, and the calcination time is 3-6 h.
The invention also provides the SAPO-34@ kaolin microsphere with the small-grain-grade pores prepared by the preparation method, and preferably, the relative content of the SAPO-34 molecular sieve is 15-35 wt% in terms of relative crystallinity.
According to a specific embodiment of the present invention, the in-situ yield (mass of in-situ product after calcination)/(mass of kaolin microspheres + phosphorus pentoxide corresponding to phosphoric acid in the charge) is 55-70 wt.% for the small-grained-scale pore SAPO-34@ kaolin microsphere catalyst prepared in accordance with the present invention.
The invention also provides a method for preparing olefin from methanol, wherein the method takes a methanol aqueous solution with the concentration of 95 wt.% as a raw material, takes the small-grain-grade pore SAPO-34@ kaolin microspheres as a catalyst, and has the mass space velocity of 2.5h at normal pressure and the reaction temperature of 450 ℃ under the condition of normal pressure-1Under conditions to produce an olefin.
The technical scheme of the invention has the following advantages:
according to the invention, kaolin microspheres are simultaneously used as a substrate and part of raw materials, so that all silica-alumina sources required for synthesizing the SAPO-34 molecular sieve are provided, and a specific mesoporous template agent is added in the synthesis process, so that the SAPO-34@ kaolin microsphere catalyst with high SAPO-34 molecular sieve content, small crystal grains and hierarchical pores is obtained; compared with the product obtained without adding the mesoporous template agent, the product has higher yield of in-situ products.
The small-grain-grade pore SAPO-34@ kaolin microsphere catalyst can be directly used as an MTO catalyst and used for an MTO reaction device, so that the preparation path of the catalyst can be greatly shortened, the preparation cost of the catalyst is reduced, the grain size and the mesoporous content of the SAPO-34 can be modulated by modulating the synthesis conditions, the structural characteristics of a composite material are modulated, the defect that the pore channels of a molecular sieve are blocked by a substrate or a binder in a semisynthesis method is avoided, the generation of a large amount of ex-situ products can be avoided, the synergistic effect of small grains and a grade pore structure is exerted, and the MTO reaction life and the selectivity of diene (ethylene and propylene) are improved.
Drawings
FIG. 1 is an XRD spectrum of the catalyst obtained in example 1.
Fig. 2a and 2b are Field Emission Scanning Electron Microscope (FESEM) photographs of the composite obtained in example 1 at 400 and 10000 magnifications, respectively.
Fig. 3 is an XRD spectrum of the catalyst obtained in example 2.
Fig. 4a and 4b are FESEM photographs of the composite obtained in example 2 at 800 x and 10000 x magnification, respectively.
Fig. 5 is an XRD spectrum of the catalyst obtained in example 3.
Fig. 6a and 6b are FESEM photographs of the composite obtained in example 3 at 500 x and 10000 x magnification, respectively.
Fig. 7 is an XRD spectrum of the catalyst obtained in example 4.
Fig. 8a and 8b are FESEM photographs of the composite obtained in example 4 magnified 2000 times and 10000 times, respectively.
Fig. 9 is an XRD spectrum of the catalyst obtained in example 5.
Fig. 10a and 10b are FESEM photographs of the composite obtained in example 5 at 500 x and 20000 x magnification, respectively.
Fig. 11 is an XRD spectrum of the catalyst obtained in example 6.
Fig. 12a and 12b are FESEM photographs of the composite obtained in example 6 at 2000 x and 20000 x magnification, respectively.
Fig. 13 is an XRD spectrum of the catalyst obtained in example 7.
Fig. 14a and 14b are 700-fold and 50000-fold FESEM photographs, respectively, of the composite material obtained in example 7.
Fig. 15 is an XRD spectrum of the catalyst obtained in comparative example 1.
Fig. 16a and 16b are FESEM photographs of the composite obtained in comparative example 1 at 1500 times and 20000 times, respectively.
Fig. 17 is an XRD spectrum of the catalyst obtained in comparative example 2.
Fig. 18a and 18b are FESEM photographs of the composite obtained in comparative example 2 at 1500 x and 20000 x magnification, respectively.
Fig. 19 is an XRD spectrum of the catalyst obtained in comparative example 3.
Fig. 20a and 20b are FESEM photographs magnified 2400 times and 20000 times, respectively, of the composite material obtained in comparative example 3.
N of sample in FIG. 212-adsorption-desorption profile.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The method adopts XRD to determine the crystal phase structure of a sample; determining the crystal morphology of the crystal form of the sample by adopting FESEM; the texture properties of the samples were determined using N2-adsorption desorption.
The content of the SAPO-34 molecular sieve in the small-crystal-grain step-hole SAPO-34@ kaolin microsphere catalyst provided by the invention is calculated according to relative crystallinity data. The relative crystallinity refers to the area ratio of the characteristic peak of each molecular sieve in the in-situ crystallization product to the characteristic peak of the corresponding molecular sieve standard sample, and the characteristic peak of the SAPO-34 molecular sieve is the peak at 2 theta which is 9.5 degrees, 16.0 degrees, 20.5 degrees and 31 degrees. The standard sample molecular sieve is a conventional microporous SAPO-34 molecular sieve produced by south China Kayaki catalyst factory, and the crystallinity of the molecular sieve is determined to be 100%.
The in situ yield and ex situ relative yield provided by the present invention are calculated by the following formulas: the in-situ yield is the mass of the SAPO-34@ kaolin microsphere catalyst after roasting the stripper/(the mass of the charged kaolin microspheres + the mass of the phosphorus pentoxide corresponding to the charged phosphoric acid), and the ex-situ relative yield is the ex-situ product mass/the mass of the SAPO-34@ kaolin microsphere catalyst.
Example 1
The embodiment provides a preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, which comprises the following steps of:
100g of kaolin is added with 350g of water and 40g of alumina sol to be uniformly mixed, the mixture is sprayed, dried and sieved to obtain 80-110 mu m kaolin microspheres, and the kaolin microspheres are roasted for 4 hours at 700 ℃ for standby.
0.5g of dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride (TPOAC) was weighed into a beaker containing 15g of water and stirred for 12 hours to dissolve it sufficiently to obtain solution A.
Weighing 4g of phosphoric acid and 15g of water, mixing, stirring for 30min at 40 ℃ in a water bath, adding 4g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres, 0.1g of Cetyl Trimethyl Ammonium Bromide (CTAB), standing for 1h at 70 ℃ in a water bath, adding the solution A, obtaining reactant gel, wherein the molar ratio of each component in the prepared gel meets the following requirements: 0.20SiO2:1Al2O3:1.7P2O5:3.9R1:0.13(R2+R3):170H2O。
Transferring the reactant gel into a sealed high-pressure crystallization kettle, and crystallizing for 40 hours in a rotary oven at 180 ℃.
And taking out the product, standing and settling for 2min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying for 4h at 100 ℃, and roasting for 6h at 600 ℃ to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere catalyst.
According to XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 15%, the yield of the in-situ product is 55%, the XRD diffraction pattern of the microspherical catalyst is shown in figure 1, the FESEM pictures are shown in figures 2a and 2b, and the size of SAPO-34 grains is about 380 nm.
Example 2
The embodiment provides a preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, which comprises the following steps of:
100g of kaolin is added with 350g of water and 35g of silica sol to be uniformly mixed, the mixture is sprayed, dried and screened to obtain 80-110 mu m kaolin microspheres, and the kaolin microspheres are roasted for 4 hours at 800 ℃ for standby.
0.7g of TPOAC was weighed into a beaker containing 10g of water and stirred for 12h to dissolve it sufficiently to give solution A.
Weighing 4g of phosphoric acid, mixing with 10g of water, stirring for 30min at 40 ℃ in a water bath, adding 4g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres, 0.3g of CTAB, standing for 2h at 75 ℃ in a water bath, and adding the solution A to obtain a reactant gel, wherein the molar ratio of each component in the prepared gel meets the following requirements: 0.25SiO2:1.17Al2O3:1.7P2O5:3.9R1:0.22(R2+R3):114H2O。
Transferring the reactant gel into a sealed high-pressure crystallization kettle, and crystallizing for 48 hours in a rotary oven at 200 ℃.
And taking out the product, standing and settling for 5min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying for 6h at 100 ℃, and roasting for 6h at 600 ℃ to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere catalyst.
According to XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 20%, the in-situ yield is 57%, the XRD diffraction pattern of the microspherical catalyst is shown in figure 3, the FESEM pictures are shown in figure 4a and figure 4b, and the size of SAPO-34 grains is about 360 nm.
Example 3
The embodiment provides a preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, which comprises the following steps of:
100g of kaolin is added with 350g of water and 40g of alumina sol to be uniformly mixed, the mixture is sprayed, dried and sieved to obtain 80-110 mu m kaolin microspheres, and the kaolin microspheres are roasted for 4 hours at 850 ℃ for standby.
0.17g of dimethylhexadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride (TPHAC) was weighed into a beaker containing 10g of water and stirred for 12 hours to dissolve it sufficiently to obtain solution A.
Weighing 5g of phosphoric acid, mixing with 10g of water, stirring for 30min at 40 ℃ in a water bath, adding 5g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres and 0.5g of Dodecyl Trimethyl Ammonium Bromide (DTAB), standing for 2.5h at 70 ℃ in a water bath, adding the solution A to obtain a reactant gel, wherein the molar ratio of each component in the prepared gel meets the following requirements: 0.26SiO2:1.20Al2O3:2.16P2O5:5.0R1:0.196(R2+R3):115H2O。
Transferring the reactant gel into a sealed high-pressure crystallization kettle, and crystallizing for 48 hours in a rotary oven at 200 ℃.
And taking out the product, standing and settling for 6min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying for 8h at 100 ℃, and roasting for 6h at 600 ℃ to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere catalyst.
According to XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 22%, the in-situ yield is 65%, the XRD diffraction pattern of the microspherical catalyst is shown in figure 5, the FESEM pictures are shown in figure 6a and figure 6b, and the SAPO-34 crystal grain size is about 350 nm.
Example 4
The embodiment provides a preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, which comprises the following steps of:
100g of kaolin is added with 350g of water and 40g of water glass and evenly mixed, the mixture is sprayed, dried and screened to obtain kaolin microspheres with the particle size of 80-110 mu m, and the kaolin microspheres are roasted for 3 hours at 900 ℃ for standby.
0.8g of TPOAC was weighed into a beaker containing 15g of water and stirred for 12h to dissolve it sufficiently to obtain solution A.
Weighing 5g of phosphoric acid, mixing with 15g of water, stirring for 30min at 40 ℃ in a water bath, adding 5g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres and 0.8g of Tetradecyl Trimethyl Ammonium Bromide (TTAB), standing for 3h at 70 ℃ in a water bath, adding the solution A, obtaining reactant gel, wherein the molar ratio of each component in the prepared gel meets the following requirements: 0.27SiO2:1.25Al2O3:2.16P2O5:5.0R1:0.40(R2+R3):292H2O。
Transferring the reactant gel into a sealed high-pressure crystallization kettle, and crystallizing for 48 hours in a rotary oven at 200 ℃.
And taking out the product, standing and settling for 8min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying at 120 ℃ for 10h, and roasting at 600 ℃ for 6h to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere catalyst.
According to XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 25%, the in-situ yield is 56%, the XRD diffraction pattern of the microspherical catalyst is shown in figure 7, the FESEM pictures are shown in figures 8a and 8b, and the size of SAPO-34 grains is about 470 nm.
Example 5
The embodiment provides a preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, which comprises the following steps of:
100g of kaolin is added with 350g of water and 40g of alumina sol to be uniformly mixed, the mixture is sprayed, dried and screened to obtain kaolin microspheres with the particle size of 80-110 mu m, and the kaolin microspheres are roasted for 4 hours at 800 ℃ for later use.
1.0g of TPOAC was weighed into a beaker containing 15g of water and stirred for 12h to dissolve it sufficiently to give solution A.
Weighing 4g of phosphoric acid, mixing with 15g of water, stirring for 30min at 40 ℃ in a water bath, adding 4g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres, 0.8g of CTAB, standing for 3.5h at 70 ℃ in a water bath, adding the solution A to obtain reactant gel, wherein the molar ratio of each component in the prepared gel meets the following requirements: 0.25SiO2:1.17Al2O3:1.73P2O5:3.9R1:0.42(R2+R3):170H2O。
Transferring the reactant gel into a sealed high-pressure crystallization kettle, and crystallizing for 48 hours in a rotary oven at 200 ℃.
And taking out the product, standing and settling for 15min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying at 120 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere catalyst.
According to XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 34%, the in-situ yield is 68%, the XRD diffraction pattern of the microspherical catalyst is shown in figure 9, the FESEM pictures are shown in figure 10a and figure 10b, and the size of SAPO-34 grains is about 600 nm.
Example 6
The embodiment provides a preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, which comprises the following steps of:
100g of kaolin is added with 350g of water and 40g of alumina sol to be uniformly mixed, the mixture is sprayed, dried and screened to obtain kaolin microspheres with the particle size of 80-110 mu m, and the kaolin microspheres are roasted for 4 hours at 800 ℃ for later use.
1.7g of TPOAC was weighed into a beaker containing 15g of water and stirred for 12h to dissolve it sufficiently to obtain solution A.
6g of phosphoric acid are weighed and mixed with 15g of water, 4Stirring for 30min under the condition of water bath at 0 ℃, adding 6g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres and 1g of CTAB, standing for 3.5h under the condition of water bath at 70 ℃, adding the solution A to obtain reactant gel, wherein the molar ratio of each component in the prepared gel meets the following requirements: 0.25SiO2:1.17Al2O3:2.6P2O5:5.9R1:0.61(R2+R3):300H2O。
Transferring the reactant gel into a sealed high-pressure crystallization kettle, and crystallizing for 48 hours in a rotary oven at 200 ℃.
And taking out the product, standing and settling for 15min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying at 120 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere catalyst.
By XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 30%, and the in-situ yield is 62%. The XRD diffractogram of the microspherical catalyst is shown in FIG. 11, the FESEM pictures are shown in FIGS. 12a and 12b, and the SAPO-34 crystal grain size is about 550 nm.
Example 7
The embodiment provides a preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst, which comprises the following steps of:
100g of kaolin is added with 350g of water and 40g of alumina sol to be uniformly mixed, the mixture is sprayed, dried and screened to obtain kaolin microspheres with the particle size of 80-110 mu m, and the kaolin microspheres are roasted for 4 hours at 800 ℃ for later use.
1.0g of TPOAC was weighed into a beaker containing 15g of water and stirred for 12h to dissolve it sufficiently to give solution A.
Weighing 5g of phosphoric acid, mixing with 15g of water, stirring for 30min at 40 ℃ in a water bath, adding 5g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres, 0.8g of CTAB, standing for 3.5h at 70 ℃ in a water bath, adding the solution A to obtain reactant gel, wherein the molar ratio of each component in the prepared gel meets the following requirements: 0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0.42(R2+R3):292H2O。
Transferring the reactant gel into a sealed high-pressure crystallization kettle, and crystallizing for 48 hours in a rotary oven at 200 ℃.
And taking out the product, standing and settling for 15min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying at 110 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere catalyst.
According to XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 35%, the in-situ yield is 70%, the XRD diffraction pattern of the microspherical catalyst is shown in figure 13, the FESEM pictures are shown in figures 14a and 14b, and the size of SAPO-34 grains is about 260 nm.
Comparative example 1
The comparative example provides a preparation method of a SAPO-34@ kaolin microsphere catalyst, which comprises the following steps:
100g of kaolin is added with 350g of water and 40g of alumina sol to be uniformly mixed, the mixture is sprayed, dried and screened to obtain kaolin microspheres with the particle size of 80-110 mu m, and the kaolin microspheres are roasted for 4 hours at 800 ℃ for later use.
1.0g of TPOAC was weighed into a beaker containing 15g of water and stirred for 12h to dissolve it sufficiently to give solution A.
Weighing 5g of phosphoric acid, mixing with 15g of water, stirring for 30min under the condition of 40 ℃ water bath, adding 5g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres, and standing for 3.5h under the condition of 70 ℃ water bath; adding the solution A, and preparing the gel with the molar ratio of the components: 0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0.20R3:292H2O。
Transferring the obtained mixed solution into a closed high-pressure crystallization kettle, and crystallizing for 48 hours in a rotary oven at 200 ℃.
And taking out the product, standing and settling for 15min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying at 110 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the SAPO-34@ kaolin microsphere catalyst.
According to XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 19%, the in-situ yield is 70.2%, the XRD diffraction pattern of the microspherical catalyst is shown in figure 15, the FESEM pictures are shown in figures 16a and 16b, and the SAPO-34 crystal grain size is about 1 μm.
Comparative example 2
The comparative example provides a preparation method of a SAPO-34@ kaolin microsphere catalyst, which comprises the following steps:
100g of kaolin is added with 350g of water and 40g of alumina sol to be uniformly mixed, the mixture is sprayed, dried and screened to obtain kaolin microspheres with the particle size of 80-110 mu m, and the kaolin microspheres are roasted for 4 hours at 800 ℃ for later use.
Weighing 5g of phosphoric acid, mixing with 15g of water, stirring for 30min under the condition of 40 ℃ water bath, adding 15g of water and 5g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres and 0.8g of CTAB, and standing for 3.5h under the condition of 70 ℃ water bath; the molar ratio of each component in the prepared gel meets the following requirements: 0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0.22R2:292H2O。
Transferring the obtained mixed solution into a closed high-pressure crystallization kettle, and crystallizing for 48 hours in a rotary oven at 200 ℃.
And taking out the product, standing and settling for 15min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying at 110 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the SAPO-34@ kaolin microsphere catalyst.
According to XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 33%, the in-situ yield is 64.9%, the XRD diffraction pattern of the microspherical catalyst is shown in figure 17, the FESEM pictures are shown in figures 18a and 18b, and the SAPO-34 crystal grain size is about 800 nm.
Comparative example 3
The comparative example provides a preparation method of a SAPO-34@ kaolin microsphere catalyst, which comprises the following steps:
100g of kaolin is added with 350g of water and 40g of alumina sol to be uniformly mixed, the mixture is sprayed, dried and screened to obtain kaolin microspheres with the particle size of 80-110 mu m, and the kaolin microspheres are roasted for 4 hours at 800 ℃ for later use.
Weighing 5g of phosphoric acid, mixing with 15g of water, stirring for 30min under the condition of 40 ℃ water bath, adding 15g of water and 5g of triethylamine under the stirring condition, continuing stirring, adding 5g of kaolin microspheres, and standing for 3.5h under the condition of 70 ℃ water bath; each of the prepared gelsThe component molar ratio satisfies: 0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0(R2+R3):292H2O。
Transferring the obtained mixed solution into a closed high-pressure crystallization kettle, and crystallizing for 48 hours in a rotary oven at 200 ℃.
Taking out the product, standing and settling for 15min, removing the ex-situ product of the supernatant, centrifugally separating the precipitated in-situ product, washing for three times, drying at 120 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the SAPO-34@ kaolin microsphere catalyst.
According to XRD quantitative analysis, the mass content of the SAPO-34 molecular sieve in the product is 11.2%, the in-situ yield is 54.2%, the XRD diffraction pattern of the microspherical catalyst is shown in figure 19, the FESEM pictures are shown in figures 20a and 20b, and the SAPO-34 crystal grain size is about 2 microns.
Experimental example: texture property and catalytic performance of small-crystal SAPO-34@ kaolin microsphere catalyst
Texture properties were tested using a Congta full-automatic specific surface and pore size analyzer (Autosorb-iQ3-XR) with nitrogen as the adsorbed gas, and N was performed on the small-grain-size pore SAPO-34@ kaolin microspherical catalyst (denoted as S @ KCT) prepared in example 7, the SAPO-34@ kaolin microspherical catalyst (denoted as S @ KT) prepared in comparative example 1, the SAPO-34@ kaolin microspherical catalyst (denoted as S @ KC) prepared in comparative example 2, and the SAPO-34@ kaolin microspherical catalyst (denoted as S @ K) prepared in comparative example 32Characterization of adsorption and desorption, N2The adsorption-desorption curve is shown in fig. 21, and the texture properties are shown in table 1. As can be seen from table 1, the simple introduction of the mesoporous template R2, namely cetyl trimethyl ammonium bromide, does not greatly affect the mesopores of the product, but as can be seen from the FESEM photograph thereof, the small-grained SAPO-34 molecular sieve distributed on the surface of the kaolin microspheres shows that the introduction of CTAB contributes to the generation of small grains; if the mesoporous template agent R3, namely TPOAC, is simply introduced, a large amount of mesoporous structures appear in the product, the volume ratio of mesopores to micropores is up to 3.2, however, the FESEM photo shows that the SAPO-34 on the surface of the kaolin microspheres has larger particle size. If CTAB and TPOAC are added simultaneously, it can be clearly seen that the synthesized product has a simple structureThe advantages of introducing two mesoporous templates, namely, the generation of a large amount of mesopores and the generation of SAPO-34 with small crystal grains, are achieved, and therefore the SAPO-34@ kaolin microsphere catalyst with the small-grain-grade pores is successfully obtained.
TABLE 1 texture Properties of the samples
Figure BDA0001635192780000131
Performing MTO catalytic reaction evaluation on the four catalysts S @ K, S @ KC, S @ KT and S @ KCT, wherein the evaluation raw material is a 95 wt.% methanol aqueous solution, and the evaluation conditions are as follows: the reaction temperature is 450 ℃, and the mass space velocity is 2.5h-1The carrier gas flow rate was 20 ml/min. The product after reaction is analyzed by off-line gas chromatography, and is detected by a northern 3420A gas chromatograph, an HP PLOT-Q column and an FID detector. When the methanol conversion was below 98 wt.%, the catalyst was considered deactivated, at which point the experiment was stopped and the time point was taken as the catalyst life. The product selectivity results are the maximum value of sampling points in the reaction process of preparing the olefin from the methanol. The evaluation results are shown in table 2.
As can be seen from the data given in Table 2, compared with the simple introduction of a mesoporous structure, the small-crystal SAPO-34@ kaolin microsphere prepared simply has better MTO reaction performance, wherein compared with the catalyst S @ K without a mesoporous template, the small-crystal SAPO-34@ kaolin microsphere catalyst S @ KC has relatively high diene selectivity and reaction life, and the diene selectivity of the hierarchical-pore SAPO-34@ kaolin microsphere catalyst S @ KT is equivalent to that of the catalyst S @ K, but the catalytic life is slightly prolonged. The obtained small-grain-grade pore SAPO-34@ kaolin microsphere catalyst has the optimal MTO reaction performance by adding the double-mesoporous template, so that the catalytic life is greatly prolonged to be close to 200min, the diene selectivity is also up to 81 percent, and the small grains and the gradient pores play a synergistic role.
TABLE 2 evaluation results of catalytic performances of methanol to olefins
Figure BDA0001635192780000141
The experimental results show that the small-crystal SAPO-34@ kaolin microsphere catalyst which has small molecular sieve crystal grains, high molecular sieve content, high in-situ product yield and a hierarchical pore structure can be prepared by the method; meanwhile, the grain size and the mesoporous content of the SAPO-34 can be modulated by modulating synthesis conditions; compared with the SAPO-34@ kaolin microsphere catalyst prepared without adding the mesoporous template, the product obtained by the method has better activity stability, long service life of the catalyst which is up to about 200min, diene selectivity which is up to 81 percent, and good industrial application prospect.

Claims (21)

1. A preparation method of a small-grain-grade pore SAPO-34@ kaolin microsphere catalyst comprises the following steps:
(1) preparing kaolin microspheres, and roasting to obtain activated kaolin microspheres;
(2) mixing the activated kaolin microspheres, water, a phosphorus source, a microporous template and a mesoporous template to prepare a reactant gel, wherein the molar ratio of the components meets the following conditions:
(0.20-0.30)SiO2:(0.58-1.85)Al2O3:(1.5-3.1)P2O5:(3.5-6.5)R1:(0.1-0.7)(R2+R3):(100-300)H2o; wherein R1 is a microporous template, R2 and R3 are mesoporous templates, and the silicon source and the aluminum source are both from kaolin microspheres;
wherein the process of preparing the reactant gel by mixing the activated kaolin microspheres, water, a phosphorus source, a microporous template and a mesoporous template comprises the following steps:
mixing the mesoporous template R3 with part of water, stirring overnight to fully dissolve the mesoporous template R3 to obtain a solution A;
uniformly mixing a phosphorus source and part of water, adding a microporous template agent R1, uniformly mixing, adding the activated kaolin microspheres obtained in the step (1), then adding a mesoporous template agent R2, stirring to fully mix, and adding the solution A to prepare reactant gel;
the mesoporous template R2 is selected from one of cationic surfactants cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium bromide;
the mesoporous template R3 is selected from one of organosilane dimethylhexadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride and dimethyloctadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride;
(3) crystallizing the reactant gel, and performing centrifugal separation to obtain a small-grain-grade-hole SAPO-34@ kaolin microsphere composite material;
(4) and roasting the small-grain-grade-hole SAPO-34@ kaolin microsphere composite material to obtain the small-grain-grade-hole SAPO-34@ kaolin microsphere catalyst.
2. The production method according to claim 1, wherein the step (1) includes the operations of: mixing kaolin, a binder and water, preparing kaolin microspheres by spray drying, and roasting to obtain activated kaolin microspheres.
3. The preparation method according to claim 2, wherein the mass ratio of the kaolin to the binder is 2.5-3: 1.
4. The production method according to claim 2, wherein the binder is a mixture of one or more of water glass, aluminum sol, and silica sol.
5. The preparation method as claimed in claim 2, wherein the roasting temperature is 700-900 ℃, and the roasting time is 1-6 h.
6. The preparation method of claim 5, wherein the roasting temperature is 800 ℃, and the roasting time is 3-4 h.
7. The method according to claim 2, wherein the kaolin microspheres have a particle size of 80-110 μm.
8. The production method according to claim 1,
in the step (2), the mol ratio of each component is (0.2-0.27) SiO2:(1-1.25)Al2O3:(1.7-2.6)P2O5:(3.9-5.9)R1:(0.13-0.61)(R2+R3):(114-300)H2O。
9. The preparation method according to claim 1, wherein, in the step (2), the aging treatment is performed after the mesoporous templating agent R2 is added.
10. The method of claim 9, wherein the temperature of the aging treatment is 40 to 90 ℃.
11. The production method according to claim 9, wherein the temperature of the aging treatment is 70 ℃.
12. The method of claim 1, wherein the solution a is added after aging for 0-5 hours.
13. The method according to claim 12, wherein the solution a is added after aging for 3.5 hours.
14. The production method according to any one of claims 1 and 8 to 13, wherein the micropore template is triethylamine.
15. The production method according to any one of claims 1, 8 to 13, wherein the phosphorus source is orthophosphoric acid.
16. The preparation method as claimed in claim 1, wherein, in the step (3), the temperature of the crystallization treatment is 180-220 ℃; the crystallization treatment time is 24-72 h;
in the step (4), the roasting temperature is 500-650 ℃, and the roasting time is 3-6 h.
17. The production method according to claim 16, wherein, in the step (3), the temperature of the crystallization treatment is 200 ℃.
18. The production method according to claim 16, wherein, in the step (3), the time of the crystallization treatment is 48 hours.
19. A small crystallite-size pore SAPO-34@ kaolin microsphere catalyst prepared according to the preparation method of any one of claims 1 to 18.
20. The small grain size pore SAPO-34@ kaolin microsphere catalyst of claim 19, wherein the relative content of SAPO-34 molecular sieve is 15-35 wt.% and the in situ product yield is 55-70 wt.% in relative crystallinity.
21. A method for preparing olefin from methanol, wherein the method takes a methanol aqueous solution with the concentration of 95 wt.% as a raw material, takes the small-grain-grade pore SAPO-34@ kaolin microsphere catalyst of claim 19 or 20 as a catalyst, and has the mass space velocity of 2.5h at the reaction temperature of 450 ℃ and the normal pressure-1Under conditions to produce an olefin.
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