CN110255579B - Metal modified hollow SAPO-34 molecular sieve and preparation method and application thereof - Google Patents

Metal modified hollow SAPO-34 molecular sieve and preparation method and application thereof Download PDF

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CN110255579B
CN110255579B CN201910530082.3A CN201910530082A CN110255579B CN 110255579 B CN110255579 B CN 110255579B CN 201910530082 A CN201910530082 A CN 201910530082A CN 110255579 B CN110255579 B CN 110255579B
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trimethyl ammonium
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CN110255579A (en
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程士敏
罗金玲
胡晓倩
孙洪平
李盛鹏
王闯
袁龙
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Chia Tai Energy Materials Dalian Co ltd
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    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
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    • 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
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Abstract

The invention discloses a metal modified hollow SAPO-34 molecular sieve, a preparation method and application thereof. The preparation method adopts cheap organic amine as a template agent, introduces structural auxiliary agents and metal elements, and carries out crystallization under the traditional hydrothermal condition. The synthesized SAPO-34 molecular sieve has high crystallinity, the average grain size is 2-10 um, the surface of the SAPO-34 molecular sieve is partially transparent, and the internal cubic hollow structure is favorable for the diffusion and mass transfer of reactants and products in catalytic reaction. The synthesized SAPO-34 molecular sieve catalyst is used for the reaction of preparing low-carbon olefin by converting methanol or dimethyl ether, has high selectivity of ethylene and propylene, and has the characteristic of long service life. The method has simple and quick process and low cost, and is suitable for industrial amplification application.

Description

Metal modified hollow SAPO-34 molecular sieve and preparation method and application thereof
Technical Field
The invention relates to the field of preparation and application of molecular sieves, in particular to a metal modified hollow SAPO-34 molecular sieve and a preparation method and application thereof.
Background
In the eighties of the last century, patent US4440871 discloses a series of silicoaluminophosphate molecular sieves SAPO-n, wherein SAPO-34 molecular sieves have attracted much attention from basic research to industrial application, and SAPO-34 has been proved to be a good industrial catalyst for preparing olefins from Methanol (MTO). The synthesis of SAPO-34 molecular sieves in US4310440 and US4440871 mainly uses tetraethylammonium hydroxide template, which is expensive. Chinese patents ZL93112230, ZL93112015 and ZL94110059 disclose methods for preparing SAPO-34 by taking triethylamine, diethylamine or a mixture of triethylamine and diethylamine as a template agent, wherein the template agent is low in price and beneficial to industrial production, but by using the template agent, cubic SAPO-34 grains with larger sizes and complete shapes are usually obtained, the crystallinity is poor, the service life in MTO reaction is short, and the selectivity of olefin products is poor.
The performance of SAPO-34 molecular sieve catalyst still needs to be improved continuously, mainly reflected in the service life of the catalyst and the selectivity to low-carbon olefins such as ethylene, propylene and the like. In order to improve the performance of the molecular sieve, the method is mainly realized by regulating and controlling the acidic property of the molecular sieve, optimizing the pore size and pore distribution, improving the crystallinity of the molecular sieve, controlling the grain size, reducing the internal diffusion, and the like. The method is characterized by using a new synthesis method, selecting different raw materials, adopting different templates, adjusting a crystallization process, preparing a hierarchical pore structure, reducing the grain size, performing molecular sieve post-treatment and the like to improve the performance of the catalyst.
Metal modification is a method for improving the acidity of SAPO-34 and modifying the pore size thereof. Patent CN1167654A discloses that SAPO-34 is modified by Cu, Co, Ni, Ca, Ba or Sr, and metal is introduced into SAPO-34 molecular sieve by direct in-situ synthesis or impregnation method to form MeAPSO-34 metal silicoaluminophosphate molecular sieve, and the modified SAPO-34 molecular sieve has better catalytic activity. Patent CN201510051260.6 discloses a method for modifying SAPO molecular sieve with metal, which is prepared by placing molecular sieve in solution containing metal ions for ion exchange, and shows higher selectivity of ethylene and propylene and longer service life in the reaction of preparing olefin from methanol.
The small-grain molecular sieve has obvious advantages in the aspects of diffusion and mass transfer, and the small-grain SAPO-34 molecular sieve can effectively prolong the service life of the catalyst and is always concerned by researchers. The literature shows that catalyst life can be significantly extended by making nano-scale SAPO-34 (grain size less than 1um) (applied. catalysts. a: General,2009,362,193), but synthesizing small-grain SAPO-34 molecular sieves typically requires expensive tetraethylammonium hydroxide as a templating agent (patents WO2003/048042, WO2003/048043, Chemistry of Materials,2008,20,2956). In addition, patents CN201110175349.5 and CN201310326018.6 respectively provide a method for preparing a small-grain SAPO-34 molecular sieve, the median diameter of the molecular sieve particles is less than 800nm, wherein the former adopts in-situ high-temperature supplementary raw materials in the crystallization process, and the latter adopts a method of processing the SAPO-34 molecular sieve into small grains and then performing secondary crystallization, and these methods have high requirements on operation and more complex processes. Therefore, the synthesis cost of the SAPO-34 with small crystal grains is high or the preparation method is complex, in addition, the difficulty of centrifugal recovery of the molecular sieve product is increased due to the small size of the SAPO-34, and particularly, when the production is amplified, the small crystal grains inevitably put forward high requirements on the production process and equipment, so that the problem of low product yield is easily caused.
The effective increase of mass transfer effect is the key to improve the service life and catalytic performance of the molecular sieve, and small crystal grains are only one of the methods. Patent CN201310489100.0 provides a method for preparing a hierarchical pore SAPO-34 molecular sieve with a microporous and macroporous composite structure, which has a hollow morphology, greatly prolongs the MTO life, and improves the ethylene selectivity, but the method requires the addition of a specific solute of hydrogen fluoride, and the strong corrosivity and harm to human body obviously do not favor practical application. In the patent CN201510334437.3, polyethylene glycol is introduced in the process of synthesizing SAPO-34, and the SAPO-34 molecular sieve with a hollow hierarchical pore structure is prepared, wherein the ratio of raw materials to Al2O 3: P2O5 is 4-8: 1, the aluminum-phosphorus basic proportion in the SAPO-34 molecular sieve structure is obviously deviated (close to 1), namely, the method has the problems of large excess and waste of aluminum raw materials, and in addition, the XRD result in the patent attached figure 1 shows that the synthesized SAPO-34 has a shoulder-coated peak around 21 degrees, is an obvious heterogeneous phase, and can influence the practical performance of the molecular sieve. The two patents provide methods for preparing the hollow hierarchical pore SAPO-34 molecular sieve, the shape of crystal grains is mainly in a conventional cubic shape, the interior of the crystal grains is in a hollow hierarchical pore structure, and the method has the characteristic of prolonging the service life of a catalyst.
In conclusion, various problems exist in the synthesis and collection processes of the SAPO-34 molecular sieve in the prior art, the catalytic performance is influenced by the large crystallization degree of the crystal grains of some molecular sieves, but the yield is low due to the small crystal grains which are difficult to collect, the process of some synthesis processes is complex, and the cost of other technical routes is high.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, provide a metal modified hollow SAPO-34 molecular sieve and a preparation method and application thereof, simultaneously meet various requirements of simple, high-efficiency, excellent quality, low price and the like in the synthesis and collection process, and the prepared molecular sieve catalyst has excellent ethylene and propylene selectivity and service life in the MTO reaction.
In order to solve the technical problems, the invention provides a metal modified hollow SAPO-34 molecular sieve which is characterized by having a structure with a partially transparent surface and a cubic hollow interior.
The invention also provides a preparation method of the metal modified hollow SAPO-34 molecular sieve, which is characterized by comprising the following steps of:
(a) mixing and stirring a phosphorus source, an aluminum source, a silicon source, water, an organic amine template agent R, a structural assistant S and a metal compound M to form a uniform gel mixture;
(b) transferring the obtained gel mixture into a reaction kettle, sealing, performing hydrothermal crystallization under the self pressure, after crystallization is finished, performing centrifugal separation on the product, washing to be neutral, and drying to obtain the metal modified hollow SAPO-34 molecular sieve raw powder.
Preferably, in step (a), the phosphorus source is selected from one or more of orthophosphoric acid, polyphosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate; the aluminum source is selected from one or more of pseudo-boehmite, activated alumina, aluminum hydroxide and aluminum isopropoxide; the silicon source is selected from one or more of silica sol, white carbon black, ethyl orthosilicate and methyl orthosilicate; the organic amine template R is selected from one or more of triethylamine, diethylamine, morpholine, di-n-propylamine and diisopropylamine.
Preferably, in step (a), the molar ratio of the raw materials in the gel mixture is the phosphorus source: an aluminum source: silicon source: organic amine template agent R: structural auxiliary agent S: a metal compound M: h2O is 0.5-2: 1: 0.1-0.5: 1-6: 0.00001-0.01: 0.001-0.1: 30 to 100, the phosphorus source is P2O5The aluminum source is calculated as Al2O3The silicon source is SiO2The metal compound M is calculated by metal atoms.
Preferably, in the step (a), the structural assistant S is one or more of dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide. The structural auxiliary agent plays an important role in forming the specific morphology of the molecular sieve, and in the technology of the invention, although the use amount of the structural auxiliary agent is small, if the structural auxiliary agent is not used, the structural morphology with a partially transparent surface and a hollow interior is not generated.
Preferably, in step (a), the metal compound M is one or more of an oxide, an inorganic salt or an organic acid salt of a metal such as magnesium, calcium, strontium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, or germanium. In the technology of the invention, the metal not only can play a role in modifying the acidity of the molecular sieve and modifying the size of an orifice, but also is beneficial to improving the crystallization quality of the molecular sieve and the crystallization rate, and in addition, the introduction of the metal element has an auxiliary effect on the formation of an internal cubic hollow structure by the molecular sieve crystal grains.
Preferably, in step (b), the crystallization conditions are: crystallizing at 150-180 deg.C for 1-12 hr, and then heating to 180-220 deg.C for crystallizing for 1-12 hr.
The invention also provides application of the metal modified hollow SAPO-34 molecular sieve, which is characterized in that the metal modified hollow SAPO-34 molecular sieve is used as a catalyst in a reaction for preparing low-carbon olefin by converting methanol or dimethyl ether.
Preferably, the specific method for applying the metal modified hollow SAPO-34 molecular sieve to the reaction of preparing the low-carbon olefin by converting the methanol or the dimethyl ether comprises the following steps: roasting the molecular sieve raw powder at 400-700 ℃ for 2-12 hours to remove a template agent, tabletting, crushing, sieving, and collecting particles with the size of 20-40 meshes as a molecular sieve catalyst; the catalyst particles are filled in a fixed bed reactor, the temperature of the reactor is controlled, methanol or dimethyl ether materials are introduced for reaction, and the products are subjected to online chromatographic detection and quantitative analysis.
The invention achieves the following beneficial effects:
(1) the metal modified hollow SAPO-34 molecular sieve provided by the invention has the advantages that the crystal grains are several microns in size (the median particle size is 2-10 um), the size is large, the collection is easy, meanwhile, the surface of the molecular sieve crystal grains is partially transparent, and the interior of the molecular sieve crystal grains has a typical cubic hollow structure, so that the molecular sieve crystal grains have a good internal mass transfer effect, the diffusion path is shortened, the mass transfer rate of reactants, intermediate species and products is improved, and the reaction life can be prolonged. Therefore, the molecular sieve can also have the characteristics of simple process for recovering large crystal grains and long service life of the catalyst due to easy diffusion inside the crystal grains.
(2) The method uses a relatively cheap template agent and carries out reaction under the conventional hydrothermal condition, the crystallization process is fast, and the crystallinity of the molecular sieve product is high, so the method has simple process and low cost.
(3) The molecular sieve and the preparation method provided by the invention simultaneously meet various requirements of simplicity, high efficiency, excellent quality, low price and the like in the synthesis and collection processes, and the prepared molecular sieve catalyst has excellent ethylene and propylene selectivity and service life in the MTO reaction.
Drawings
FIG. 1 is an X-ray diffraction pattern of SAPO-34 molecular sieves synthesized in example 1 (FIG. 1a), example 6 (FIG. 1b), example 7 (FIG. 1c), and comparative example 1 (FIG. 1 d);
FIGS. 2 and 3 are electron microscope result graphs of SAPO-34 molecular sieve synthesized in example 1;
FIG. 4 is an electron microscope result chart of SAPO-34 molecular sieve synthesized in example 7;
FIG. 5 is an electron microscope result chart of SAPO-34 molecular sieve synthesized by comparative example 1;
FIG. 6 is an electron microscope result chart of SAPO-34 molecular sieve synthesized by comparative example 2.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
In a molar ratio of P2O5：Al2O3：SiO2：R：S：M：H2O is 1: 1: 0.2: 3: 0.0005: 0.03: 50, weighing the materials, wherein an organic amine template agent R is a mixture of triethylamine and diisopropylamine (the molar ratio of the triethylamine to the diisopropylamine is 2: 1), a structural assistant S is Cetyl Trimethyl Ammonium Bromide (CTAB), and a metal compound M is a mixture of zinc acetate, magnesium acetate and cobalt chloride (the molar ratio of the zinc acetate to the magnesium acetate to the cobalt chloride is 1: 1: 1). Mixing deionized water, pseudo-boehmite, phosphoric acid, silica sol, a template agent R, a structural assistant S and a metal compound M, stirring for 2 hours, uniformly transferring to a hydrothermal reaction kettle, sealing, crystallizing at 170 ℃ for 8 hours, and then raising the temperature to 200 ℃ for crystallizing for 8 hours. After crystallization is finished, cooling the reaction kettle to room temperature, then centrifugally separating a crystallized product from a mother solution, washing a solid product to be neutral by using deionized water, and finally drying to obtain SAPO-34 molecular sieve raw powder. The X-ray diffraction result is shown in figure 1(a), the SAPO-34 molecular sieve structure with good crystallization degree is shown, the electron microscope result is shown in figures 2 and 3, the molecular sieve is mainly cubic crystal grains, the size of the molecular sieve is 2-4 um, the surface of the molecular sieve is partially transparent, the molecular sieve is visible from a small amount of cracked molecular sieve, and the interior of the molecular sieve is a typical cubic hollow structure.
Then roasting the molecular sieve raw powder for 5 hours at 600 ℃, tabletting and granulating, screening out 20-40 mesh particles, weighing 2.5g of the particles, placing the particles in a fixed bed reactor, activating the particles for 1 hour at 550 ℃, then cooling to 450 ℃, feeding by using a micro pump, wherein the raw material is 40% methanol aqueous solution, and the airspeed is 3.5 hours-1The reaction product was subjected to on-line chromatographic analysis for the fixed bed activity evaluation of methanol-to-low carbon olefins (MTO), and the selectivity and lifetime of ethylene and propylene are shown in table 1.
Example 2
The same as example 1, except that the amount of CTAB as a raw material structure auxiliary agent is changed to 0.00001, and the organic amine template agent R is single triethylamine, namely the molar ratio P2O5：Al2O3：SiO2：R：CTAB：M：H2O is 1: 1: 0.2: 3: 0.00001: 0.03: and (5) 50 preparing materials. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 1.5-4 mu m, the surface of the molecular sieve is partially transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 3
As in example 1, except that the raw material metal compound M is a mixture of zinc acetate and magnesium acetate (molar ratio of both is 1: 1), i.e., in terms of molar ratio P2O5：Al2O3：SiO2：R：CTAB：M：H2O is 1: 1: 0.2: 3: 0.0005: 0.03: 50 ingredients are added, and in addition, the crystallization is firstly carried out for 8 hours at 170 ℃, and then the crystallization is carried out for 6 hours after the temperature is raised to 200 ℃. The X-ray diffraction result shows that the molecular sieve is a SAPO-34 molecular sieve structure with good crystallization, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 1-3.5 mu m, the surface of the molecular sieve is partially transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 4
The same as example 1 except that the ratio of the raw material silica sol was changed to 0.15, and the raw material metal compound M was a mixture of copper nitrate and manganese acetate (molar ratio of both was 1: 1), i.e., in a molar ratio P2O5：Al2O3：SiO2：R：CTAB：M：H2O is 1: 1: 0.15: 3: 0.0005: 0.03: 50 ingredients are added, and in addition, the crystallization is firstly carried out for 12 hours at 160 ℃, and then the crystallization is carried out for 12 hours after the temperature is raised to 190 ℃. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 1.5-6 um, the surface of the molecular sieve is partially transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 5
Same as example 1, except that the CTAB amount of the raw material is changed to 0.0001, and the original amount isThe metal compound M is a mixture of zinc sulfate and titanium sulfate (the molar ratio of the zinc sulfate to the titanium sulfate is 1: 1), namely the molar ratio P2O5：Al2O3：SiO2：R：CTAB：M：H2O is 1: 1: 0.2: 3: 0.0001: 0.03: and (5) 50 preparing materials. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 2.5-6 um, the surface of the molecular sieve is partially transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 6
The same as example 1 except that the ratio of the raw material silica sol was changed to 0.3, the raw material metal compound M was zinc nitrate, and the ratio thereof was changed to 0.01, that is, the molar ratio P2O5：Al2O3：SiO2：R：CTAB：M：H2O is 1: 1: 0.3: 3: 0.0005: 0.01: and (5) 50 preparing materials. The X-ray diffraction result is shown in figure 1(b), the molecular sieve is a crystallized SAPO-34 molecular sieve structure, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 2-8 um, the surface of the molecular sieve is locally transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in table 1.
Example 7
As in example 5, except that the raw material metal compound M is a mixture of manganese acetate and magnesium acetate (molar ratio of the two is 1: 1), i.e., in terms of molar ratio P2O5：Al2O3：SiO2：R：CTAB：M：H2O is 1: 1: 0.2: 3: 0.0001: 0.03: and (5) 50 preparing materials. The X-ray diffraction result is shown in figure 1(c), the molecular sieve is a crystallized SAPO-34 molecular sieve structure, the electron microscope result is shown in figure 4, the molecular sieve is mainly cubic crystal grains, the size of the molecular sieve is 2.5-6 um, the surface of the molecular sieve is partially transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in table 1.
Example 8
In the same example 1, except that the consumption of CTAB as the raw material is changed to 0.01, the metal compound M as the raw material is changed to calcium nitrate, the proportion is changed to 0.05, and the organic amine template R is single diethylamine, namely, the mol ratio P2O5：Al2O3：SiO2：R：CTAB：M：H2O is 1: 1: 0.2: 3: 0.01: 0.05: and (5) 50 preparing materials. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 5.5-10 mu m, the surface of the molecular sieve is partially transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 9
In the same example 1, except that the ratio of the raw material silica sol was changed to 0.1, the raw material structural assistant S was changed to cetyltrimethylammonium chloride (CTAC), the ratio thereof was changed to 0.01, the raw material metal compound M was changed to nickel nitrate, the ratio thereof was changed to 0.001, and the organic amine template R was a mixture of morpholine and diisopropylamine (molar ratio of the two was 2: 1), that is, the molar ratio P was changed2O5：Al2O3：SiO2：R：CTAC：M：H2O is 1: 1: 0.1: 3: 0.01: 0.001: 50 ingredients are added, and in addition, the crystallization is firstly carried out for 12 hours at 150 ℃, and then the crystallization is carried out for 12 hours after the temperature is raised to 180 ℃. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 2-7 mu m, the surface of the molecular sieve is locally transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 10
In the same example 2, except that the ratio of the raw material silica sol was changed to 0.5, the raw material structure assistant S was changed to tetradecyltrimethylammonium chloride (TTAC), the raw material metal compound M was changed to copper sulfate, and the ratio was changed to 0.1, that is, the molar ratio P was2O5：Al2O3：SiO2：R：TTAC：M：H2O is 1: 1: 0.5: 3: 0.00001: 0.1: 50 ingredients are added, and in addition, the crystallization is firstly carried out for 10 hours at 150 ℃, and then the crystallization is carried out for 2 hours at 220 ℃. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 2.5-8.5 mu m, the surface of the molecular sieve is locally transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 11
Same as example 10, except that tetradecane, a structural auxiliary of the raw material, is usedThe ratio of trimethyl ammonium chloride (TTAC) is 0.0001, the raw material metal compound M is a mixture of chromium nitrate and germanium dioxide (the molar ratio of the two is 1: 1), and the ratio of raw material water is 100, namely the molar ratio P2O5：Al2O3：SiO2：R：TTAC：M：H2O is 1: 1: 0.5: 3: 0.0001: 0.1: 100, proportioning. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 3-10 mu m, the surface of the molecular sieve is locally transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 12
In the same example 3, only the aluminum source material was changed to aluminum hydroxide, the silicon source material was changed to ethyl orthosilicate, and the structural assistant S was changed to Dodecyl Trimethyl Ammonium Chloride (DTAC), i.e., in terms of molar ratio P2O5：Al2O3：SiO2：R：DTAC：M：H2O is 1: 1: 0.2: 3: 0.0005: 0.03: and (5) 50 preparing materials. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 1-4 mu m, the surface of the molecular sieve is locally transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 13
In the same example 12, except that the ratio of the raw material phosphoric acid was changed to 2, the raw material silicon source was changed to silica, the ratio of the raw material organic amine template agent R was changed to 6, and the ratio of the raw material water was changed to 100, that is, the molar ratio P was changed2O5：Al2O3：SiO2：R：DTAC：M：H2O is 2: 1: 0.2: 6: 0.0005: 0.03: 100 portions, in addition, the crystallization is firstly performed at 150 ℃ for 10 hours, and then the crystallization is performed at 200 ℃ for 6 hours. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 4-12 mu m, the surface of the molecular sieve is locally transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 14
Same as example 5, except that the phosphorus source of the raw material was changedAmmonium hydrogen phosphate, the proportion of which is 0.5, the raw material aluminum source is changed into aluminum isopropoxide, the raw material structure auxiliary agent S is changed into Octadecyl Trimethyl Ammonium Bromide (OTAB), the total proportion of the organic amine template agent R is changed into 1, wherein the mixing molar proportion of triethylamine and diisopropylamine is changed into 1: 2, the proportion of raw material water is changed to 30, namely the molar ratio P2O5：Al2O3：SiO2：R：OTAB：M：H2O ═ 0.5: 1: 0.2: 1: 0.0001: 0.03: and (3) preparing the materials. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 1-4 mu m, the surface of the molecular sieve is locally transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Example 15
In the same example 5, only the aluminum source material was changed to aluminum isopropoxide, the silicon source material was changed to ethyl orthosilicate, and the structural assistant S was changed to Octadecyl Trimethyl Ammonium Bromide (OTAB) in a ratio of 0.01, i.e., in a molar ratio of P2O5：Al2O3：SiO2：R：OTAB：M：H2O is 1: 1: 0.2: 3: 0.01: 0.03: 50 ingredients are added, and in addition, the crystallization is firstly performed for 1 hour at 180 ℃, and then the crystallization is performed for 1 hour after the temperature is raised to 220 ℃. The X-ray diffraction result shows that the molecular sieve is an SAPO-34 molecular sieve structure with good crystallinity, the electron microscope result shows that the molecular sieve is mainly cubic crystal grains with the size of 1.5-5 mu m, the surface of the molecular sieve is partially transparent, the interior of the molecular sieve is a cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Comparative example 1
In the same manner as in example 3 except that CTAB was not added during the compounding and that no metal compound was added, and in addition, crystallization was carried out at 170 ℃ for 10 hours, followed by raising to 200 ℃ for 10 hours. The X-ray diffraction results are shown in fig. 1(d), which shows that the molecular sieve is not well crystallized, which is obviously inferior to the examples, and in addition, diffraction signals of impurity crystal phases appear at 7.5 degrees, the electron microscope results are shown in fig. 5, which shows that the molecular sieve has smooth surface, no transparent morphology, very uneven grain size, and the fixed bed activity evaluation results are shown in table 1.
Comparative example 2
As in example 3, except that CTAB was not added during compounding. The X-ray diffraction result shows that the molecular sieve is of an SAPO-34 molecular sieve structure, the electron microscope result is shown in FIG. 6, the molecular sieve is smooth in surface and has no transparent appearance, and the fixed bed activity evaluation result is shown in Table 1.
Comparative example 3
The same as example 3, except that no metal compound was added during the compounding, and the crystallization was performed by first crystallizing at 170 ℃ for 10 hours, and then crystallizing at 200 ℃ for 10 hours. The X-ray diffraction result shows that the molecular sieve is of an SAPO-34 molecular sieve structure, but the crystallization is poor, in addition, the electron microscope result shows that the surface of the molecular sieve has no transparent appearance, the interior of the molecular sieve has no cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Comparative example 4
As in example 5, except that CTAB was not added during compounding. The X-ray diffraction result shows that the molecular sieve is of an SAPO-34 molecular sieve structure, the electron microscope result shows that the surface of the molecular sieve is smooth and has no transparent appearance, and the activity evaluation result of the fixed bed is shown in Table 1.
Comparative example 5
The same as example 5, except that no metal compound was added during the compounding process. The X-ray diffraction result shows that the molecular sieve is of an SAPO-34 molecular sieve structure, but the crystallization is poor, in addition, the electron microscope result shows that the surface of the molecular sieve has no transparent appearance, the interior of the molecular sieve has no cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
Comparative example 6
Same as example 9 except that no CTAC was added during compounding. The X-ray diffraction result shows that the molecular sieve is of an SAPO-34 molecular sieve structure, the electron microscope result shows that the surface of the molecular sieve is smooth and has no transparent appearance, and the activity evaluation result of the fixed bed is shown in Table 1.
Comparative example 7
The same as example 10, except that no metal compound was added during the compounding process. The X-ray diffraction result shows that the molecular sieve is of an SAPO-34 molecular sieve structure, but the crystallization is poor, in addition, the electron microscope result shows that the surface of the molecular sieve has no transparent appearance, the interior of the molecular sieve has no cubic hollow structure, and the activity evaluation result of the fixed bed is shown in Table 1.
TABLE 1 MTO reaction fixed bed evaluation results for molecular sieves
Figure BDA0002099463270000121
Figure BDA0002099463270000131
Wherein the service life is the time for maintaining the conversion rate of the methanol to be more than 99.95 percent, and the index of the service life is selected.
The technical means disclosed in the invention scheme are not limited to the technical means disclosed in the above embodiments, but also include the technical scheme formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.

Claims (7)

1. The preparation method of the metal modified hollow SAPO-34 molecular sieve is characterized by comprising the following steps of:
(a) mixing and stirring a phosphorus source, an aluminum source, a silicon source, water, an organic amine template agent R, a structural assistant S and a metal compound M to form a uniform gel mixture; the structural auxiliary agent S is one or more of dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide;
(b) transferring the obtained gel mixture into a reaction kettle, sealing, performing hydrothermal crystallization under self pressure, after crystallization is finished, performing centrifugal separation and washing on the product to be neutral, and drying to obtain the metal modified hollow SAPO-34 molecular sieve raw powder which has a structure with a partially transparent surface and a cubic hollow interior.
2. The method for preparing a metal-modified hollow SAPO-34 molecular sieve of claim 1, wherein in step (a), the source of phosphorus is selected from one or more of orthophosphoric acid, polyphosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate; the aluminum source is selected from one or more of pseudo-boehmite, activated alumina, aluminum hydroxide and aluminum isopropoxide; the silicon source is selected from one or more of silica sol, white carbon black, ethyl orthosilicate and methyl orthosilicate; the organic amine template R is selected from one or more of triethylamine, diethylamine, morpholine, di-n-propylamine and diisopropylamine.
3. The method for preparing a metal-modified hollow SAPO-34 molecular sieve of claim 1, wherein in step (a), the molar ratio of each raw material in the gel mixture is phosphorus source: an aluminum source: silicon source: organic amine template agent R: structural auxiliary agent S: a metal compound M: h2O = 0.5-2: 1: 0.1-0.5: 1-6: 0.00001-0.01: 0.001-0.1: 30 to 100, the phosphorus source is P2O5The aluminum source is calculated as Al2O3The silicon source is SiO2The metal compound M is calculated by metal atoms.
4. The method for preparing a metal-modified hollow SAPO-34 molecular sieve of claim 1, wherein in step (a), the metal compound M is one or more of an oxide, an inorganic salt or an organic acid salt of a metal selected from the group consisting of magnesium, calcium, strontium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, and germanium.
5. The method for preparing a metal-modified hollow SAPO-34 molecular sieve according to claim 1, wherein in step (b), the crystallization conditions are: crystallizing at 150-180 deg.C for 1-12 hr, and then heating to 180-220 deg.C for crystallizing for 1-12 hr.
6. The application of the metal modified hollow SAPO-34 molecular sieve prepared by the preparation method of any one of claims 1 to 5, which is used as a catalyst in the reaction of preparing low carbon olefin by converting methanol or dimethyl ether.
7. The application of the metal modified hollow SAPO-34 molecular sieve of claim 6, wherein the specific method for applying the metal modified hollow SAPO-34 molecular sieve to the reaction of preparing low carbon olefin by converting methanol or dimethyl ether comprises the following steps: roasting the molecular sieve raw powder at 400-700 ℃ for 2-12 hours to remove a template agent, tabletting, crushing, sieving, and collecting particles with the size of 20-40 meshes as a molecular sieve catalyst; the catalyst particles are filled in a fixed bed reactor, the temperature of the reactor is controlled, methanol or dimethyl ether materials are introduced for reaction, and the products are subjected to online chromatographic detection and quantitative analysis.
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