CN116199237A - Small-grain SAPO-34 molecular sieve, preparation method and application thereof, and method for preparing olefin from methanol - Google Patents

Small-grain SAPO-34 molecular sieve, preparation method and application thereof, and method for preparing olefin from methanol Download PDF

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CN116199237A
CN116199237A CN202111453652.7A CN202111453652A CN116199237A CN 116199237 A CN116199237 A CN 116199237A CN 202111453652 A CN202111453652 A CN 202111453652A CN 116199237 A CN116199237 A CN 116199237A
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molecular sieve
sapo
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郭磊
朱伟平
邢爱华
李飞
郭智慧
袁德林
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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National Institute of Clean and Low Carbon Energy
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
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    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
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    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C07C2529/82—Phosphates
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    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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Abstract

The invention relates to the field of molecular sieves, and discloses a small-grain SAPO-34 molecular sieve, a preparation method and application thereof. The method comprises the following steps: (1) Mixing an aluminum source, a high-silicon SAPO-34 molecular sieve, a template agent and water, and then performing pretreatment to obtain initial gel; (2) And mixing the initial gel with a silicon source and a phosphorus source to obtain a mixed solution, and aging, hydrothermal crystallization and roasting the mixed solution to obtain the small-grain SAPO-34 molecular sieve. The preparation method does not need to add expensive template agent or other organic additives, and the process is easy to operate and easy to realize industrial application. The preparation method can greatly improve the synthesis yield of the molecular sieve while obtaining the small-grain molecular sieve with uniform granularity distribution.

Description

Small-grain SAPO-34 molecular sieve, preparation method and application thereof, and method for preparing olefin from methanol
Technical Field
The invention relates to the field of molecular sieves, in particular to a small-grain SAPO-34 molecular sieve, and a preparation method and application thereof.
Background
In 1984, the united states Union Carbide Corporation (UCC) developed silicoaluminophosphate series molecular Sieves (SAPOs). The molecular sieve is a crystalline silicoaluminophosphate, and the three-dimensional framework structure is formed by PO 2+ 、AlO 2- And SiO 2 Tetrahedral structure. Wherein, the SAPO-34 framework structure is a CHA structure, and the main pore canal is an eight-membered ring structure. Due to the proper acidity and pore canal structure, the catalyst has excellent catalytic performance in the reaction of preparing olefin (MTO) from methanol, and is the MTO catalyst which is most widely used at present.
However, due to the structure of the small-pore big cage, the SAPO-34 molecular sieve is easy to quickly accumulate carbon in the MTO reaction and is extremely easy to inactivate. Meanwhile, the method has the problem that diffusion is limited in the reaction process, so that the catalytic performance is reduced.
The reduction of the particle size of the molecular sieve not only can improve the external specific surface area and increase the number of the pore openings on the external surface, thereby improving the specific activity of the molecular sieve, but also is beneficial to shortening the diffusion path of reactants and products, weakening the diffusion limit, further improving the carbon deposition resistance of the catalyst and prolonging the service life of the catalyst. At present, the average particle size of the SAPO-34 molecular sieve synthesized by a conventional method is generally 5-20 mu m. How to effectively reduce the particle size of the SAPO-34 molecular sieve is a hot spot of current research.
CN104340986a discloses a method for preparing small crystal SAPO-34 molecular sieve, which is to pretreat SAPO-34 molecular sieve into particles with granularity of 10-800nm as crystallization precursor; mixing an organic amine template agent, water and optional silicon source, aluminum source and phosphorus source to prepare crystallization liquid, carrying out hydrothermal crystallization on a crystallization precursor and the crystallization liquid, and finally separating to obtain the small-grain SAPO-34 molecular sieve.
CN104445266a discloses a preparation method of small-grain SAPO-34 molecular sieve, which mainly solves the problem of large grain size of the SAPO-34 molecular sieve obtained by the traditional synthesis method, and is characterized in that the synthesis of the small-grain molecular sieve is promoted by adding crystal seeds with defective structures. The technical scheme mainly comprises the following steps: 1. carrying out hydrothermal crystallization on an initial crystallization liquid of the SAPO-34 molecular sieve at 200-250 ℃ for 1-10h, and carrying out solid-liquid separation to obtain SAPO-34 seed crystals with more lattice defects; 2. the seed crystal is added into the initial crystallization liquid of the SAPO-34, and after the seed crystal is subjected to hydrothermal treatment for 0.1 to 4 hours at the temperature of 140 to 170 ℃, the seed crystal can be dissolved into fine fragments which finally play a role of structure guiding and crystal nucleus, and then the temperature is increased to 180 to 250 ℃ to continue the hydrothermal crystallization, so that the small-grain SAPO-34 molecular sieve product is obtained.
CN105585022a discloses a method for preparing a flaky nano SAPO-34 molecular sieve, which is prepared by adding a specific organic additive into gel mixed by an aluminum source, a phosphorus source, a silicon source, a template agent and water, uniformly stirring, adding the nano SAPO-34 molecular sieve as a seed crystal, and crystallizing at a variable temperature.
The preparation of small-grain SAPO-34 molecular sieves in the prior art, especially in industrial application processes, mainly comprises the following defects: (1) Tetraethyl ammonium hydroxide (TEAOH) and the like are adopted as template agents or specific organic additives are added, so that the production cost is greatly increased; (2) Complex synthesis process, difficult control of final product composition, low synthesis yield of molecular sieve, etc.
Disclosure of Invention
The invention aims to solve the problems that a specific template agent or other auxiliary agents are needed in the process of preparing a small-grain SAPO-34 molecular sieve and the grain size of the prepared SAPO-34 molecular sieve is large in the prior art, and provides the small-grain SAPO-34 molecular sieve, and a preparation method and application thereof. The preparation method can greatly improve the synthesis yield of the molecular sieve while obtaining the small-grain molecular sieve with uniform granularity distribution.
To achieve the above object, a first aspect of the present invention provides a method for preparing a small-grained SAPO-34 molecular sieve, characterized in that the method comprises the steps of:
(1) Mixing an aluminum source, a high-silicon SAPO-34 molecular sieve, a template agent and water, and then performing pretreatment to obtain initial gel;
(2) And mixing the initial gel with a silicon source and a phosphorus source to obtain a mixed solution, and aging, hydrothermal crystallization and roasting the mixed solution to obtain the small-grain SAPO-34 molecular sieve.
The second aspect of the present invention provides a small-grained SAPO-34 molecular sieve prepared by the above-described preparation method.
The third aspect of the invention provides an application of the small-grain SAPO-34 molecular sieve in preparing olefin from methanol.
In a fourth aspect, the present invention provides a method for preparing olefins from methanol, comprising: in the presence of protective gas, methanol and molecular sieve are subjected to contact reaction;
the molecular sieve is the small-grain SAPO-34 molecular sieve.
Through the technical scheme, the small-grain SAPO-34 molecular sieve, the preparation method and application thereof, and the method for preparing olefin from methanol have the following beneficial effects:
in the invention, the aluminum source and the high-silicon SAPO-34 molecular sieve are pretreated in the presence of the template agent and water, and the initial gel for constructing the primary structure and the active element of the molecular sieve framework is further formed by controlling the proportion of the template agent and the water, and the silicon source and the phosphorus source are further added for crystallization on the basis, so that the small-grain SAPO-34 molecular sieve can be prepared.
Further, the average grain diameter of the small-grain SAPO-34 molecular sieve provided by the invention is 0.5-1.5 mu m, the grain size of the molecular sieve is uniform, the synthesis yield of the molecular sieve is high, the synthesis yield of the molecular sieve is more than 80%, and the industrial application is easy to realize. When used for the reaction of preparing olefin from methanol, the catalyst can show longer catalytic life and higher low-carbon olefin selectivity.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the molecular sieves prepared in examples 1-3 and comparative examples 1-3;
FIG. 2 is a Scanning Electron Micrograph (SEM) of the molecular sieve prepared in example 1;
FIG. 3 is a Scanning Electron Micrograph (SEM) of the molecular sieve prepared in example 2;
FIG. 4 is a Scanning Electron Micrograph (SEM) of the molecular sieve prepared in example 3;
FIG. 5 is a Scanning Electron Micrograph (SEM) of the molecular sieve prepared in example 8;
FIG. 6 is a Scanning Electron Micrograph (SEM) of the molecular sieve prepared in comparative example 1;
FIG. 7 is a Scanning Electron Micrograph (SEM) of the molecular sieve prepared in comparative example 2;
FIG. 8 is a Scanning Electron Micrograph (SEM) of the molecular sieve prepared in comparative example 3;
FIG. 9 is a Scanning Electron Micrograph (SEM) of the molecular sieve prepared in comparative example 4;
FIG. 10 is a Scanning Electron Micrograph (SEM) of the molecular sieve prepared in comparative example 5.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a preparation method of a small-grain SAPO-34 molecular sieve, which is characterized by comprising the following steps:
(1) Mixing an aluminum source, a high-silicon SAPO-34 molecular sieve, a template agent and water, and then performing pretreatment to obtain initial gel;
(2) And mixing the initial gel with a silicon source and a phosphorus source to obtain a mixed solution, and aging, hydrothermal crystallization and roasting the mixed solution to obtain the small-grain SAPO-34 molecular sieve.
In the invention, the aluminum source and the high-silicon SAPO-34 molecular sieve are pretreated in the presence of the template agent and water, and the initial gel for constructing the primary structure and the active element of the molecular sieve framework is further formed by controlling the proportion of the template agent and the water, and the silicon source and the phosphorus source are further added for crystallization on the basis, so that the small-grain SAPO-34 molecular sieve can be prepared, and the molecular sieve has high synthesis yield.
According to the invention, the Si/Al of the high-silicon SAPO-34 molecular sieve is 0.4-0.6.
According to the invention, the SAPO-34 molecular sieve with the Si/Al can form an effective active unit or primary structure under the alkaline condition of the template agent and water, and can play a role in guiding seed crystals while providing part of Si source to induce the synthesis of the small-grain SAPO-34 molecular sieve.
According to the invention, the aluminum source, the high silicon SAPO-34 molecular sieve, the template agent, the water, the silicon source and the phosphorus source are used in amounts such that the molar ratio of the component materials in the mixed solution is: aR bSiO 2 :Al 2 O 3 :cP 2 O 5 :dH 2 O, wherein R is a template agent, and a is more than or equal to 0.5 and less than or equal to 8; b is more than or equal to 0.1 and less than or equal to 1; c is more than or equal to 0.1 and less than or equal to 2.5; d is more than or equal to 5 and less than or equal to 20;0.3<a/d<0.6。
Further, the aluminum source, the high silicon SAPO-34 molecular sieve, the template agent, the water, the silicon source and the phosphorus source are used in an amount such that the molar ratio of the materials of each component in the mixed solution is as follows: aR bSiO 2 :Al 2 O 3 :cP 2 O 5 :dH 2 O, wherein R is a template agent, and a is more than or equal to 2 and less than or equal to 6; b is more than or equal to 0.2 and less than or equal to 0.5; c is more than or equal to 0.8 and less than or equal to 1.5; d is more than or equal to 10 and less than or equal to 15;0.4<a/d<0.5。
According to the invention, the pretreatment temperature is 30-80 ℃, and the pretreatment time is 2-48h.
In the invention, under the above conditions, the mixture containing the aluminum source, the high-silicon SAPO-34 molecular sieve, the template agent and the water is pretreated, so that the reaction precursor can be activated to form the silicon and aluminum primary unit with higher reactivity, and the SAPO-34 molecular sieve with small crystal grains and high yield is obtained.
Further, the temperature of the pretreatment is 40-70 ℃, and the time of the pretreatment is 12-36h.
According to the invention, the aging conditions include: the aging time is 2-48h, and the aging temperature is 30-80 ℃.
Further, the aging conditions include: the aging time is 6-24h, and the aging temperature is 40-60 ℃.
According to the present invention, the conditions for hydrothermal crystallization include: the hydrothermal crystallization temperature is 170-210 ℃, and the hydrothermal crystallization time is 6-40h.
Further, the hydrothermal crystallization conditions include: the hydrothermal crystallization temperature is 180-200 ℃, and the hydrothermal crystallization time is 6-40h.
According to the invention, the conditions of the calcination include: the roasting temperature is 500-700 ℃ and the roasting time is 2-12h.
Further, the roasting conditions include: the roasting temperature is 550-650 ℃ and the roasting time is 6-8h.
According to the present invention, the phosphorus source is selected from at least one of phosphoric acid, phosphorous acid and phosphorus pentoxide.
According to the present invention, the aluminum source is selected from at least one of pseudo-boehmite, aluminum sol and aluminum isopropoxide.
In the invention, the content of the aluminum oxide in the aluminum sol is 10-30wt%.
According to the present invention, the silicon source is selected from at least one of silica sol, tetraethyl orthosilicate, and active silica.
In the invention, the content of silicon dioxide in the silica sol is 10-40wt%.
According to the invention, the template agent is at least one selected from triethylamine, diisopropylamine, diethylamine, morpholine, N-diisopropylethylamine, cyclohexylamine and N-butylamine.
In the invention, the method further comprises the following steps: and washing, filtering and drying the product after hydrothermal crystallization by adopting deionized water. The specific operating steps and conditions for washing, filtering and drying may be carried out according to conventional procedures in the art.
In one embodiment of the invention, the small-grain SAPO-34 molecular sieve is prepared according to the following steps:
(1) Uniformly mixing an aluminum source, a high-silicon SAPO-34 molecular sieve and water, adding a template agent, stirring at 20-60 ℃ for 0.5-36h, and then transferring into a reaction kettle with a polytetrafluoroethylene lining for pretreatment to obtain initial gel;
(2) And cooling the initial gel to room temperature, adding a silicon source under stirring, stirring for 0.5-24h, adding a phosphorus source, continuously stirring for 0.5-24h to obtain a mixed solution, ageing and hydrothermally crystallizing the mixed solution, washing, filtering and drying the hydrothermally crystallized product by adopting deionized water, and roasting in an air atmosphere to obtain the small-grain SAPO-34 molecular sieve.
The second aspect of the present invention provides a small-grained SAPO-34 molecular sieve prepared by the above-described preparation method.
According to the present invention, the small-grained SAPO-34 molecular sieve has an average particle size of 0.5-1.5 μm.
In the invention, the average grain diameter of the small-grain SAPO-34 molecular sieve is 0.5-1.5 mu m, and the grain size of the molecular sieve is uniform, so that the industrial application is easy to realize. When used for the reaction of preparing olefin from methanol, the catalyst can show longer catalytic life and higher low-carbon olefin selectivity.
Further, the average particle size of the small-grain SAPO-34 molecular sieve is 0.5-1 μm.
The third aspect of the invention provides an application of the small-grain SAPO-34 molecular sieve in preparing olefin from methanol.
When the small-grain SAPO-34 molecular sieve is used for the reaction of preparing olefin from methanol, the small-grain SAPO-34 molecular sieve can show longer catalytic life and higher low-carbon olefin selectivity.
In a fourth aspect, the present invention provides a method for preparing olefins from methanol, comprising: in the presence of protective gas, methanol and molecular sieve are subjected to contact reaction;
the molecular sieve is the small-grain SAPO-34 molecular sieve.
In the present invention, the conditions of the contact reaction include: the reaction temperature is 400-500 ℃, the reaction pressure is 0-0.2MPa, and the methanol airspeed is 1-10h -1 。
In the present invention, the shielding gas may be a shielding gas conventional in the art, such as nitrogen.
The present invention will be described in detail by examples. In the following examples of the present invention,
the average particle size of the small-grain SAPO-34 molecular sieve is measured by a laser particle size method, and the testing instrument is a Mastersizer 3000 laser diffraction particle size analyzer of the Markov company;
the morphology of the small-grain SAPO-34 molecular sieve is characterized by adopting a Scanning Electron Microscope (SEM);
the crystal form of the small-grain SAPO-34 molecular sieve is measured by X-ray diffraction (XRD);
the synthesis yield of the small-grain SAPO-34 molecular sieve is calculated according to the following method:
molecular sieve synthesis yield = product dry basis/raw material oxide dry basis x 100%;
the raw materials used in the examples and comparative examples are all commercially available.
Example 1
(1) 10g of pseudo-boehmite and 0.5g of high silicon SAPO-34 (Si/Al=0.5) molecular sieve are uniformly mixed with 8g of deionized water, 40.48g of triethylamine is added, and after stirring for 2 hours at room temperature, the mixture is transferred into a reaction kettle with a polytetrafluoroethylene lining and treated for 24 hours at 60 ℃.
(2) 3.41g of silica sol (30 wt%) is continuously added under stirring after the pretreated mixed gel is cooled to room temperature, 14.83g of phosphoric acid (85 wt%) is dropwise added after stirring for 1h, the mixture is obtained after continuously stirring for 1h, the mixture is aged for 2h at room temperature, and crystallization is carried out for 24h at 200 ℃. The obtained product is centrifugally washed and filtered by deionized water,And (3) after drying, roasting for 5 hours at 650 ℃ in an air atmosphere to obtain the small-grain SAPO-34 molecular sieve A1, wherein the synthesis yield of the molecular sieve is 87%. The molar ratio of the materials of each component in the mixed solution is as follows: 6R:0.26SiO 2 :Al 2 O 3 :0.96P 2 O 5 :13H 2 O, wherein a/d is 0.46.
The XRD spectrum of the small-grain SAPO-34 molecular sieve A1 is shown in figure 1, the microstructure is shown in the SEM picture of figure 2, and the SAPO-34 molecular sieve has a cubic morphology, uniform particle size and average particle size of 0.5 mu m.
As can be seen from fig. 1, the samples prepared in example 1 showed characteristic peak diffraction peaks of SAPO-34 at 2θ=9.5±0.1, 15.9±0.1, 20.5±0.1, 25.1±0.1°, indicating that the prepared samples were SAPO-34 molecular sieves having CHA topology.
Example 2
(1) 10g of pseudo-boehmite, 0.86g of high silicon SAPO-34 (Si/Al=0.6) molecular sieve and 8g of deionized water are uniformly mixed, 36.55g of diisopropylamine is added, and after stirring for 2 hours at room temperature, the mixture is transferred into a reaction kettle with a polytetrafluoroethylene lining, and the mixture is treated for 16 hours at 70 ℃.
(2) 3.41g of silica sol (30 wt%) is continuously added under stirring after the pretreated mixed gel is cooled to room temperature, 14.08g of phosphoric acid (85 wt%) is dropwise added after stirring for 1h, the mixture is obtained after continuously stirring for 1h, the mixture is aged for 2h at room temperature, and crystallization is carried out for 30h at 200 ℃. And (3) centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product in an air atmosphere at 650 ℃ for 5 hours to obtain the small-grain SAPO-34 molecular sieve A2, wherein the synthesis yield of the molecular sieve is 83%. The molar ratio of the materials of each component in the mixed solution is as follows: 5.4R:0.26SiO 2 :Al 2 O 3 :0.96P 2 O 5 :13H 2 O, wherein a/d is 0.42.
The XRD spectrum of the small-grain SAPO-34 molecular sieve A2 is shown in figure 1, the microstructure is shown in the SEM picture of figure 3, and the SAPO-34 molecular sieve has a cubic morphology, uniform particle size and average particle size of 0.65 mu m.
As can be seen from fig. 1, the samples prepared in example 2 showed characteristic peak diffraction peaks of SAPO-34 at 2θ=9.5±0.1, 15.9±0.1, 20.5±0.1, 25.1±0.1°, indicating that the prepared samples were SAPO-34 molecular sieves having CHA topology.
Example 3
(1) 27.24g of aluminum isopropoxide and 0.45g of high silicon SAPO-34 (Si/Al=0.5) molecular sieve are uniformly mixed with 8g of deionized water, 40.48g of triethylamine is added, and after stirring for 2 hours at room temperature, the mixture is transferred into a reaction kettle with a polytetrafluoroethylene lining, and the mixture is treated for 12 hours at 70 ℃.
(2) 3.41g of silica sol (30%) is continuously added under stirring after the pretreated mixed gel is cooled to room temperature, 14.83g of phosphoric acid (85%) is dropwise added after stirring for 1h, the stirring is continuously carried out for 1h to obtain a mixed solution, the mixed solution is aged for 2h at room temperature, and crystallization is carried out for 24h at 200 ℃. And (3) centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product in an air atmosphere at 650 ℃ for 5 hours to obtain the small-grain SAPO-34 molecular sieve A3, wherein the synthesis yield of the molecular sieve is 84%. The molar ratio of the materials of each component in the mixed solution is as follows: 6R:0.26SiO 2 :Al 2 O 3 :0.96P 2 O 5 :13H 2 O, wherein a/d is 0.46.
The XRD spectrum of the small-grain SAPO-34 molecular sieve A3 is shown in figure 1, the microstructure is shown in the SEM picture of figure 4, and the SAPO-34 molecular sieve has a cubic morphology, uniform particle size and average particle size of 0.55 mu m.
As can be seen from fig. 1, the samples prepared in example 3 showed characteristic peak diffraction peaks of SAPO-34 at 2θ=9.5±0.1, 15.9±0.1, 20.5±0.1, 25.1±0.1°, indicating that the prepared samples were SAPO-34 molecular sieves having CHA topology.
Example 4
(1) Uniformly mixing 10g of pseudo-boehmite, 0.90g of high silicon SAPO-34 molecular sieve (Si/Al=0.6) and 8g of deionized water, adding 35.21g of triethylamine (R1), 3.90g of diethylamine (R2), stirring at room temperature for 2h, transferring into a reaction kettle with a polytetrafluoroethylene lining, and treating at 60 ℃ for 24h.
(2) After the pretreated mixed gel was cooled to room temperature, 6.05g of silica sol (30 wt%) was continuously added under stirring, 15.26g of phosphoric acid (85%) was added dropwise after stirring for 1 hour, and after stirring was continued for 1 hour, a mixture was obtained, and the mixture was aged at room temperature for 2 hours and crystallized at 200 ℃ for 16 hours. The obtained product is centrifugally washed and filtered by deionized waterAnd (3) after drying, roasting for 5 hours at 650 ℃ in an air atmosphere to obtain the small-grain SAPO-34 molecular sieve A4, wherein the synthesis yield of the molecular sieve is 85%. The molar ratio of the materials of each component in the mixed solution is as follows: 5.2R1:0.8R2:0.30SiO 2 :Al 2 O 3 :0.85P 2 O 5 :13.3H 2 O, wherein a/d=0.45 ((0.52+0.8)/13.3=0.45).
The small-grain SAPO-34 molecular sieve A5 has a cubic structure with an average grain diameter of about 1 μm.
Example 5
(1) 10g of pseudo-boehmite and 1g of high silicon SAPO-34 molecular sieve (Si/Al=0.6) are uniformly mixed with 8.50g of deionized water, 32.21g of triethylamine is added, and after stirring for 2 hours at room temperature, the mixture is transferred into a reaction kettle with a polytetrafluoroethylene lining and treated for 24 hours at 60 ℃.
(2) After the pretreated mixed gel is cooled to room temperature, 3.50g of tetraethoxysilane is continuously added under stirring, 16.26g of phosphoric acid (85 wt%) is dropwise added after stirring for 1h, the mixture is continuously stirred for 1h to obtain a mixed solution, the mixed solution is aged for 2h at room temperature, and crystallization is carried out for 36h at 200 ℃. And (3) centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product in an air atmosphere at 650 ℃ for 5 hours to obtain the small-grain SAPO-34 molecular sieve A5, wherein the synthesis yield of the molecular sieve is 82%. The molar ratio of the materials of each component in the mixed solution is as follows: 4.8R:0.25SiO 2 :Al 2 O 3 :1.05P 2 O 5 :11.8H 2 O, wherein a/d = 0.41.
The small-grain SAPO-34 molecular sieve A5 has a cubic structure with an average grain size of 0.8 μm.
Example 6
The same method as in example 1 was used to prepare a SAPO-34 molecular sieve, wherein the Si/Al ratio of the high-silicon SAPO-34 molecular sieve was changed to 0.3, the conditions were unchanged, and a molecular sieve A6 was obtained, and the synthesis yield of the molecular sieve was 82%. The molecular sieve A6 has a cubic structure with an average particle diameter of 1.2 μm.
Example 7
The same method as in example 1 was used to prepare a SAPO-34 molecular sieve, wherein the Si/Al ratio of the high-silicon SAPO-34 molecular sieve was changed to 0.7, the conditions were unchanged, and a molecular sieve A7 was obtained, and the synthesis yield of the molecular sieve was 83%. The molecular sieve A7 has a cubic structure with an average particle diameter of 1.3 μm.
Example 8
SAPO-34 molecular sieves were prepared in the same manner as in example 1, with only the pretreatment conditions being: the molecular sieve A8 is prepared by processing for 60 hours at 100 ℃ under the same conditions, and the synthesis yield of the molecular sieve is 83%. The microscopic morphology of the SAPO-34 molecular sieve A8 is shown in an SEM photograph of FIG. 5, the average particle size of the SAPO-34 molecular sieve is 1.5 mu m, the SAPO-34 molecular sieve has a cubic morphology, and when the particle size of the molecular sieve A9 is tested by adopting a laser diffraction particle size analyzer, the particle size is in bimodal distribution, and the particle size distribution is uneven.
Example 9
The same method as in example 1 is used for preparing the SAPO-34 molecular sieve, and the addition amount of the high-silicon SAPO-34 molecular sieve is only changed to be 1.5g, and the molar ratio of the components in the mixed solution is as follows: 6R:0.20SiO 2 :Al 2 O 3 :0.95P 2 O 5 :13H 2 O, wherein a/d is 0.46, and the conditions are unchanged, so that the molecular sieve A9 is prepared, and the synthesis yield of the molecular sieve is 80%. The molecular sieve A9 has a cubic structure with an average particle size of 1.5 mu m, and when the particle size of the molecular sieve A9 is tested by a laser diffraction particle size analyzer, the particle size is in bimodal distribution, which shows that the particle size distribution is uneven.
Comparative example 1
Preparation of SAPO-34 molecular sieve by traditional hydrothermal synthesis
10g of pseudo-boehmite, 14.88g of phosphoric acid (concentration of 85 wt%) and 47.23g of deionized water were mixed and stirred, and after stirring for 1 hour, silica Sol (SiO) was added dropwise 2 7.71g of template triethylamine 19.65g is added after the mixture is uniformly stirred, the mixture is continuously stirred for 1h and aged for 2h at room temperature. The molar ratio of the materials of each component in the obtained mixture is as follows: 3R:0.6SiO 2 :1Al 2 O 3 :1P 2 O 5 :50H 2 O, wherein a/d is 0.06. Putting the gel into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization for 48 hours at 200 ℃, centrifugally washing, filtering and drying the obtained product by deionized water, and roasting for 5 hours at 650 ℃ in an air atmosphere to obtain the SAPO-34 molecular sieve D1, wherein the synthesis yield of the molecular sieve is 48%.
XRD spectrum of the SAPO-34 molecular sieve D1 is shown in figure 1, microstructure is shown in SEM photograph of figure 6, and the SAPO-34 molecular sieve has a cubic morphology and an average particle size of 7 mu m.
As can be seen from fig. 1, the samples prepared in comparative example 1 showed characteristic peak diffraction peaks of SAPO-34 at 2θ=9.5±0.1, 15.9±0.1, 20.5±0.1, 25.1±0.1°, indicating that the prepared samples were SAPO-34 molecular sieves having CHA topology.
Comparative example 2
The procedure and proportions were the same as in example 1, except that no high silicon SAPO-34 molecular sieve was added.
(1) Uniformly mixing 10g of pseudo-boehmite with 8g of deionized water, adding 40.48g of triethylamine, stirring at room temperature for 2 hours, transferring into a reaction kettle with a polytetrafluoroethylene lining, and treating at 60 ℃ for 24 hours.
(2) 3.41g of silica sol (30 wt%) is continuously added under stirring after the pretreated mixed gel is cooled to room temperature, 14.83g of phosphoric acid (85 wt%) is dropwise added after stirring for 1h, the mixture is obtained after continuously stirring for 1h, the mixture is aged for 2h at room temperature, and crystallization is carried out for 24h at 200 ℃. And (3) centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product in an air atmosphere at 650 ℃ for 5 hours to obtain the SAPO-34 molecular sieve D2, wherein the synthesis yield of the molecular sieve is 51%. The molar ratio of the materials of each component in the mixed solution is as follows: 6R:0.26SiO 2 :Al 2 O 3 :0.96P 2 O 5 :13H 2 O, wherein a/d is 0.46.
XRD spectrum of the SAPO-34 molecular sieve D2 is shown in figure 1, microstructure is shown in SEM photograph of figure 7, the SAPO-34 molecular sieve has cubic morphology, uneven particle size and average particle size of 4.5 mu m.
As can be seen from fig. 1, the samples prepared in comparative example 2 showed characteristic peak diffraction peaks of SAPO-34 at 2θ=9.5±0.1, 15.9±0.1, 20.5±0.1, 25.1±0.1°, indicating that the prepared samples were SAPO-34 molecular sieves having CHA topology.
Comparative example 3
The proportions of the ingredients were the same as in example 1, but without pretreatment.
10g of pseudo-boehmite and 0.5g of high silicon SAPO-34 (Si/Al=0.5) molecular sieve are combined with 8g of deionized waterMixing water uniformly, adding 40.48g of triethylamine, stirring at room temperature for 2 hours, continuously adding 3.41g of silica sol (30%), stirring for 1 hour, dropwise adding 14.83g of phosphoric acid (85%), continuously stirring for 1 hour to obtain a mixed solution, ageing the mixed solution at room temperature for 2 hours, and crystallizing at 200 ℃ for 24 hours. And (3) centrifugally washing, filtering and drying the obtained product by deionized water, and roasting the product in an air atmosphere at 650 ℃ for 5 hours to obtain the small-grain SAPO-34 molecular sieve D3, wherein the synthesis yield of the molecular sieve is 54%. The molar ratio of the materials of each component in the mixed solution is as follows: 6R:0.26SiO 2 :Al 2 O 3 :0.96P 2 O 5 :13H 2 O, wherein a/d is 0.46.
XRD spectrum of the synthesized SAPO-34 molecular sieve D3 is shown in figure 1, microstructure is shown in SEM photograph of figure 8, and the SAPO-34 molecular sieve has a cubic morphology and an average particle size of 3.5 mu m.
As can be seen from fig. 1, the samples prepared in comparative example 3 showed characteristic peak diffraction peaks of SAPO-34 at 2θ=9.5±0.1, 15.9±0.1, 20.5±0.1, 25.1±0.1°, indicating that the prepared samples were SAPO-34 molecular sieves having CHA topology.
Comparative example 4
The SAPO-34 molecular sieve was prepared according to the method of example 1, only the feeding sequence of the aluminum source and the silicon source was changed, and the conditions were unchanged, so as to obtain a molecular sieve D4, the synthesis yield of the molecular sieve was 52%, and the average particle size of the molecular sieve D4 was 25. Mu.m. XRD test is carried out on the molecular sieve D4, and XRD results show that the molecular sieve D4 not only has characteristic peak diffraction peaks of SAPO-34 at 2 theta=9.5+/-0.1, 15.9+/-0.1, 20.5+/-0.1 and 25.1+/-0.1 degrees, but also has characteristic peak diffraction peaks of SAPO-5 at 2 theta=7.36 degrees, which indicates that the molecular sieve D4 is not a pure phase SAPO-34 molecular sieve and contains SAPO-5 impurity phases. The microstructure of the molecular sieve D4 is shown in the SEM photograph of fig. 9, and it can be seen from fig. 9 that the molecular sieve D4 includes a SAPO-5 molecular sieve having a prismatic structure.
Comparative example 5
The SAPO-34 molecular sieve was prepared according to the method of example 1, only the feeding sequence of the aluminum source and the phosphorus source was changed, and the conditions were unchanged, so as to obtain a molecular sieve D5, the synthesis yield of the molecular sieve was 40%, and the average particle size of the molecular sieve D5 was 15. Mu.m. The microscopic morphology of the molecular sieve D5 is shown in the SEM photograph of FIG. 10, and as can be seen from FIG. 10, the non-cubic block structure in the figure is an amorphous phase, which indicates that the molecular sieve D5 is not a pure phase SAPO-34 molecular sieve.
Test example 1
The molecular sieve catalysts prepared in examples 1 to 9 and comparative examples 1 to 5 were subjected to methanol to olefin reaction evaluation using a fixed bed catalytic reaction evaluation apparatus.
The evaluation conditions were as follows: respectively weighing 0.8 g of the molecular sieve catalyst sample, putting the molecular sieve catalyst sample into a reactor, introducing nitrogen at 500 ℃ for activating for 0.5h, then cooling to 450 ℃, mixing raw material methanol solution with carrier gas-nitrogen carried by a flowmeter pump, entering a preheating furnace, vaporizing into gas in the preheating furnace, then entering the reactor for reaction, wherein the nitrogen flow rate is 14mL/min, and the methanol airspeed is 3.50h -1 The reaction products were analyzed on line using Agilent 7890B chromatography. The catalyst life was calculated as the time from the start of the reaction to 99% methanol conversion. Table 1 shows the results of specific experiments for examples and comparative examples.
TABLE 1 evaluation results of olefins produced by methanol conversion
C 2 H 4 (％) C 3 H 6 (％) C 2 H 4 +C 3 H 6 (％) C 4+ (％) C 5+ (％) Lifetime (min)
Example 1 49.53 34.84 84.37 8.66 2.62 235
Example 2 49.05 35.07 84.12 9.12 2.75 230
Example 3 49.63 33.77 83.40 8.47 2.94 230
Example 4 49.33 34.59 83.92 8.66 2.85 220
Example 5 49.21 34.47 83.68 9.01 2.31 220
Example 6 49.03 34.29 83.32 8.73 3.27 218
Example 7 48.76 34.00 82.76 9.41 2.95 215
Example 8 48.63 34.55 83.18 8.99 3.00 210
Example 9 49.01 33.98 82.99 9.58 3.06 210
Comparative example 1 47.08 34.95 82.03 9.62 2.8 135
Comparative example 2 43.63 38.28 81.91 8.5 1.62 150
Comparative example 3 47.67 34.41 82.08 9.14 3.35 155
Comparative example 4 44.52 35.45 79.97 10.80 4.98 130
Comparative example 5 40.25 33.17 73.42 13.50 6.21 90
As can be seen from the results in Table 1, the small-grain SAPO-34 molecular sieve catalyst prepared by the method of the invention can effectively shorten the diffusion of product molecules in crystal pore channels, effectively inhibit the generation of carbon deposit and prolong the service life of the catalyst compared with the SAPO-34 molecular sieve catalyst synthesized by the conventional method.
Furthermore, the small-grain SAPO-34 molecular sieve prepared by the invention can prolong the service life of the catalyst and has high diene (ethylene+propylene) selectivity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (11)

1. A method for preparing a small-grain SAPO-34 molecular sieve, comprising the steps of:
(1) Mixing an aluminum source, a high-silicon SAPO-34 molecular sieve, a template agent and water, and then performing pretreatment to obtain initial gel;
(2) And mixing the initial gel with a silicon source and a phosphorus source to obtain a mixed solution, and aging, hydrothermal crystallization and roasting the mixed solution to obtain the small-grain SAPO-34 molecular sieve.
2. The method of claim 1, wherein the high silicon SAPO-34 molecular sieve has a Si/Al of 0.4 to 0.6.
3. The production method according to claim 1 or 2, wherein the aluminum sourceThe dosages of the high-silicon SAPO-34 molecular sieve, the template agent, the water, the silicon source and the phosphorus source enable the molar ratio of the components in the mixed solution to be: aR bSiO 2 :Al 2 O 3 :cP 2 O 5 :dH 2 O, wherein R is a template agent, and a is more than or equal to 0.5 and less than or equal to 8; b is more than or equal to 0.1 and less than or equal to 1; c is more than or equal to 0.1 and less than or equal to 2.5; d is more than or equal to 5 and less than or equal to 20;0.3<a/d<0.6；
Preferably, 2.ltoreq.a.ltoreq.6; b is more than or equal to 0.2 and less than or equal to 0.5; c is more than or equal to 0.8 and less than or equal to 1.5; d is more than or equal to 10 and less than or equal to 15;0.4< a/d <0.5.
4. A production method according to any one of claims 1 to 3, wherein the temperature of the pretreatment is 30 to 80 ℃ and the time of the pretreatment is 2 to 48 hours.
5. The production method according to any one of claims 1 to 4, wherein the aging conditions include: the aging time is 2-48h, and the aging temperature is 30-80 ℃.
6. The production method according to any one of claims 1 to 5, wherein the conditions for hydrothermal crystallization include: the hydrothermal crystallization temperature is 170-210 ℃, and the hydrothermal crystallization time is 6-40h.
7. The production method according to any one of claims 1 to 6, wherein the conditions of calcination include: the roasting temperature is 500-700 ℃ and the roasting time is 2-12h.
8. The production method according to any one of claims 1 to 7, wherein the phosphorus source is selected from at least one of phosphoric acid, phosphorous acid, and phosphorus pentoxide;
preferably, the aluminum source is selected from at least one of pseudo-boehmite, aluminum sol and aluminum isopropoxide;
preferably, the silicon source is selected from at least one of silica sol, ethyl orthosilicate and active silica;
preferably, the template agent is selected from at least one of triethylamine, diisopropylamine, diethylamine, morpholine, N-diisopropylethylamine, cyclohexylamine and N-butylamine.
9. A small-grained SAPO-34 molecular sieve made by the method of any one of claims 1 to 8;
preferably, the small-grained SAPO-34 molecular sieve has an average particle size of 0.5-1.5 μm.
10. Use of the small-crystallite SAPO-34 molecular sieve of claim 9 in the production of olefins from methanol.
11. A method for producing olefins from methanol, the method comprising: in the presence of protective gas, methanol and molecular sieve are subjected to contact reaction;
the molecular sieve is the small-grain SAPO-34 molecular sieve of claim 9.
CN202111453652.7A 2021-12-01 2021-12-01 Small-grain SAPO-34 molecular sieve, preparation method and application thereof, and method for preparing olefin from methanol Pending CN116199237A (en)

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