CN115504485B - Preparation method of SAPO-17 molecular sieve - Google Patents

Preparation method of SAPO-17 molecular sieve Download PDF

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CN115504485B
CN115504485B CN202110699686.8A CN202110699686A CN115504485B CN 115504485 B CN115504485 B CN 115504485B CN 202110699686 A CN202110699686 A CN 202110699686A CN 115504485 B CN115504485 B CN 115504485B
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molecular sieve
sapo
scm
organic solvent
heat treatment
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CN115504485A (en
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乔健
袁志庆
陶伟川
王振东
滕加伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to JP2023516537A priority patent/JP2023540642A/en
Priority to KR1020237012873A priority patent/KR20230067667A/en
Priority to TW110133529A priority patent/TW202222693A/en
Priority to US18/245,202 priority patent/US20230356201A1/en
Priority to EP21866019.9A priority patent/EP4197971A4/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a preparation method of a SAPO-17 molecular sieve. The method comprises the following steps: 1) Mixing an organic template agent cR and a first organic solvent cS, and performing first heat treatment to obtain a precursor P; 2) Mixing an SCM-34 molecular sieve, a silicon source which is selectively added and a second organic solvent cS, and performing second heat treatment to obtain a mixed material M; 3) Mixing the precursor P obtained in the step 1) with the mixed material M obtained in the step 2) to form a crystallization mixture; 4) And 3) pretreating the crystallization mixture obtained in the step 3), and then carrying out crystallization reaction to obtain the SAPO-17 molecular sieve. The SAPO-17 molecular sieve synthesized by the method has excellent performance when being used for industrial production of methanol downstream products, industrial production of synthesis gas downstream products and hydrocarbon cracking.

Description

Preparation method of SAPO-17 molecular sieve
Technical Field
The invention relates to the field of preparation of molecular sieves, in particular to a preparation method of a SAPO-17 molecular sieve.
Background
Microporous molecular sieve is a kind of porous material with selective adsorption as main characteristic, and its unique pore canal system makes it possess the capacity of sieving small molecules of different sizes. And the size distribution range of the inner cavity of the materialThe method is widely applied to the fields of adsorption separation, heterogeneous catalysis, carriers of various guest molecules, ion exchange and the like, and achieves excellent technical effects. Conventional zeolite molecular sieves are crystalline silicate materials, typically composed of silica tetrahedra [ SiO ] 4 ] 4- And an alumoxane tetrahedron [ AlO ] 4 ] 5- Are connected by a common oxygen atom and are collectively called TO 4 Tetrahedra (primary structural units) in which the silicon element may be partially isomorphously substituted with other elements, particularly with some trivalent or tetravalent elements such as B, ga, ge, ti, zeolite molecular sieves have found wide application in catalysis, adsorptive separation, ion exchange, and other fields due to their structural and chemical properties. As one of the representative materials of structure-determining properties, one key factor in the application performance of molecular sieves comes from the unique characteristics of their intrinsic channels or cavities, which are determined by the intrinsic crystal structure of the molecular sieve, so that obtaining a molecular sieve of new crystal structure is of great importance for developing the application of molecular sieves. For many years, with the continuous expansion of the application field of zeolite and the need for new properties and new performances of zeolite by scientific research development, a great deal of effort is put into the synthesis and preparation of novel zeolite molecular sieves.
In 1982, scientists Wilson S.T. and Flanigen E.M. of United states, inc. (UCC, inc.) used aluminum source, phosphorus source and organic template agent to successfully synthesize and develop a novel family of molecular sieves-aluminum phosphate molecular sieves AlPO 4 -n, n represents the model number (US 4310440). After two years, UCC company is in AlPO 4 On the basis of n, si atoms are used for partially replacing Al atoms and P atoms in an AlPO framework, and another series of silicoaluminophosphate molecular sieves SAPO-n, n representing the model (US 4440871, US 4499327) are successfully prepared. In the structure of SAPO-n, si atoms replace P or Al atoms in original AlPO to form SiO 4 、AlO 4 PO (Positive and negative) 4 Tetrahedrally composed, non-neutral molecular sieve frameworks in which silicon is present in two ways: (1) a silicon atom replaces a phosphorus atom; (2) Respectively substituted by two silicon atomsA pair of aluminum atoms and phosphorus atoms, and has certain acidity and oxidability, greatly improves the activity of catalytic application, and brings wide application prospect in the petrochemical field.
Molecular sieves of known topology are prepared by hydrothermal or solvothermal synthesis. A typical hydrothermal or solvothermal synthesis method mainly comprises the steps of firstly uniformly mixing reactants such as a metal source (aluminum source and the like), a non-metal source (silicon source, phosphorus source and the like), an organic template agent, a solvent (water, alcohol and the like) and the like to obtain an initial sol, namely a crystallization mixture, then placing the crystallization mixture into a reaction kettle with polytetrafluoroethylene as a lining and stainless steel as an outer wall, sealing, and carrying out crystallization reaction at a certain temperature and under autogenous pressure, wherein the crystallization reaction is similar to the process of earth rock formation, namely the process of precipitating molecular sieve crystals from the crystallization mixture. Specifically, for example, a synthetic silicoaluminophosphate SAPO-17 (topological structure code ERI) molecular sieve is used, the reaction mixture comprises framework reactants (such as silica sol, phosphoric acid and alumina), a Structure Directing Agent (SDA) and water, which are uniformly mixed, and the mixture is placed in a fixed-temperature oven (190-220 ℃) for a plurality of days for crystallization reaction, and when the crystallization reaction is completed, a solid product containing the ERI molecular sieve is filtered out and dried for standby. The organic amine selected for the synthesis of SAPO-17 molecular sieves is typically selected from small cyclic amines, such as quinuclidine (Intrazeolite Chemistry,1983, vol218, P79), piperidine (Acta Crystallographica Section C Crystal Structure Communications,1986, vol42, P283), and cyclohexylamine (Solid State Nuclear Magnetic Resonance,1992, vol1, P137), among others. As synthesis technology advances, templates including N, N' -tetramethyl-1, 6-hexamethylenediamine (Comptes Rendus Chimie,2005, vol8, p 531), neopentanamine (ChemSusChem, 2011,Vol4,P91), etc., have been introduced into the synthesis system of SAPO-17 molecular sieves. And because of the pore topology of SAPO-17 molecular sieves and the appropriate B acid sites (Catalysis, 1992, vol9, P1), researchers have used them as catalysts for MTO (methanol to olefins) reactions. US4499327 discloses that water is used as diluent and the weight hourly space velocity is not more than 1h -1 Under the same conversion conditions, the SAPO-17 molecular sieve has higher ethylene and higher ethylene content than SAPO-34 and SAPO-56Propylene ratio. Literature [ chemical New Material, 2015,43,166 ] and literature [ Studies in Surface Science and Catalysis,1994,81,393 ] also use SAPO-17 as a catalyst for methanol to olefins reactions in the presence of large amounts of diluents and at low space velocities (less than 1h -1 ) Higher ethylene to propylene ratios are also obtained.
The development of new methods for preparing SAPO-17 molecular sieves has also been the subject of ongoing research in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel method for preparing the SAPO-17 molecular sieve, and the SAPO-17 molecular sieve synthesized by the method has excellent performance when being used for industrial production of downstream products of methanol, industrial production of downstream products of synthesis gas and hydrocarbon cracking.
The first aspect of the invention provides a method for preparing a SAPO-17 molecular sieve, comprising the following steps:
1) Mixing an organic template agent cR and a first organic solvent cS, and performing first heat treatment to obtain a precursor P;
2) Mixing an SCM-34 molecular sieve, a silicon source which is selectively added and a second organic solvent cS, and performing second heat treatment to obtain a mixed material M;
3) Mixing the precursor P obtained in the step 1) with the mixed material M obtained in the step 2) to form a crystallization mixture;
4) And 3) pretreating the crystallization mixture obtained in the step 3), and then carrying out crystallization reaction to obtain the SAPO-17 molecular sieve.
Wherein the SCM-34 molecular sieve in step 2) is also a novel molecular sieve having the formula "Al 2 O 3 ：xSiO 2 ：yP 2 O 5 "the schematic chemical composition is shown, wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0.75 and less than or equal to 1.5; in XRD diffraction data of the SCM-34 molecular sieve, the 2 theta angle of the strongest peak in the range of 5-50 degrees is 7.59+/-0.2; the X-ray diffraction pattern of the SCM-34 molecular sieve comprises X-ray diffraction peaks shown in the following table:
2θ(°) relative strength, [ (I/I) 0 )×100]
7.59±0.2 50-100
10.81±0.1 10-20
16.52±0.1 5-50
17.97±0.1 5-50
23.34±0.05 5-50
34.74±0.05 5-50
Further, the X-ray diffraction pattern of the SCM-34 molecular sieve comprises X-ray diffraction peaks as shown in the following table:
2θ(°) relative strength, [ (I/I) 0 )×100]
7.59±0.2 50-100
10.81±0.1 10-20
14.25±0.1 5-50
16.52±0.1 5-50
17.97±0.1 5-50
21.01±0.1 10-20
23.34±0.05 5-50
24.27±0.05 5-50
26.05±0.05 5-50
27.82±0.05 5-50
28.15±0.02 5-50
30.03±0.02 5-50
34.74±0.02 5-50
Further, the X-ray diffraction pattern of the SCM-34 molecular sieve comprises X-ray diffraction peaks as shown in the following table:
wherein, the incident ray of X-ray diffraction is Cu K alpha 1.
Further, the preparation method of the SCM-34 molecular sieve comprises the following steps: crystallizing a mixture containing an aluminum source, a phosphorus source, an organic template agent R1, an organic template agent R2, a solvent S1, a solvent S2, a solvent S3 and a third silicon source which is selectively added to obtain an SCM-34 molecular sieve;
wherein the organic template agent R1 is selected from one or more of quaternary ammonium salt or quaternary ammonium base; r2 is selected from one or more of imidazole or pyrrolidine derivatives; the solvent S1 is one or more than one of amide solvents; the solvent S2 is one or more selected from cyclic organic solvents; s3 is selected from one or more of water or lower alcohols.
Further, the organic template agent R1 is selected from one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide and tetrabutylammonium hydroxide; the organic template agent R2 is selected from one or more of imidazole, 2-methylimidazole, 4-methylimidazole, 1- (3-aminopropyl) imidazole, 2-ethyl-4-methylimidazole, pyrrolidine, 1- (3-pyrrolidine) pyrrolidine and N-ethyl-2-aminomethylpyrrolidine; the solvent S1 is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide and N, N-dibutylformamide; the solvent S2 is one or more selected from 1, 4-dioxane, cyclohexane, cyclohexanone and cyclohexanol; the solvent S3 is selected from one or more of methanol, ethanol, glycol, butanol and water.
Further, the organic template agent R1 is preferably one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide; the organic template agent R2 is preferably one or more of 1- (3-aminopropyl) imidazole, 2-ethyl-4-methylimidazole and N-ethyl-2-aminomethylpyrrolidine; the solvent S1 is preferably one or two of N, N-dimethylacetamide and N, N-dibutylformamide; the solvent S2 is preferably one or two of 1, 4-dioxane and cyclohexanone; the solvent S3 is preferably one or both of ethanol and water, wherein water is preferably deionized water.
Further, in the mixture, the aluminum source is Al 2 O 3 Meter, third silicon source with SiO 2 Counting the phosphorus source by P 2 O 5 The molar compositions of the organic template agent R1+R2 and the solvent S1+S2+S3 are as follows: siO (SiO) 2 /Al 2 O 3 =0 to 1, preferably 0.1 to 0.75; p (P) 2 O 5 /Al 2 O 3 =0.5 to 2, preferably 0.75 to 1.5; template agent R1+R2/Al 2 O 3 =1 to 200, preferably 5 to 50; solvent S1+S2+S3/Al 2 O 3 =5 to 500, preferably 35 to 120.
Further, the molar ratio of the organic template agent R1 to the organic template agent R2 is 0.01-1: 1, preferably 0.1 to 0.25:1.
further, the molar ratio of the solvent S1, the solvent S2, and the solvent S3 is 1:0.01 to 1:1 to 100, preferably 1:0.05 to 0.5:10 to 80 percent.
Further, the aluminum source is selected from one or more of aluminum isopropoxide, aluminate, meta-aluminate, aluminum salt, hydroxide of aluminum, oxide of aluminum and mineral containing aluminum, preferably one or two of aluminate and meta-aluminate; the third silicon source is selected from one or more of organic silicon, amorphous silicon dioxide, silica sol, solid silicon oxide, silica gel, diatomite and water glass, and is preferably one or more of amorphous silicon dioxide, silica sol and solid silicon oxide; the phosphorus source is at least one selected from phosphoric acid, monoammonium phosphate and monoammonium phosphate, preferably orthophosphoric acid.
Further, in the preparation method of the SCM-34 molecular sieve, stirring and sedimentation treatment are carried out before crystallization treatment. The stirring time is 0.5-5 h, and the sedimentation treatment time is 1-12 h.
Further, in the preparation method of the SCM-34 molecular sieve, the crystallization treatment conditions include: the crystallization temperature is 120-200 ℃, preferably 140-180 ℃, more preferably 140-160 ℃; the crystallization time is 1 to 5d, preferably 3 to 5d, more preferably 4 to 5d.
Further, in the preparation method of the SCM-34 molecular sieve, the step of preparing the SCM-34 molecular sieve by conventional post-treatment, such as filtration, washing and drying, is carried out after crystallization treatment; and optionally, a step of calcining the obtained SCM-34 molecular sieve.
Further, in the step 1), the organic template agent cR is at least one of 1, 10-phenanthroline, 2-bipyridine, 4-bipyridine, piperazine, cyclohexylamine and pyridine; preferably at least one of piperazine and cyclohexylamine.
Further, in step 1) and step 2), the first organic solvent cS and the second organic solvent cS are each independently selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 2-cyclopentane epoxide, 1, 4-dioxane, cyclohexanone, cyclohexanol; preferably at least one of 1, 4-dioxane and cyclohexanone.
Further, the mass ratio of the added SCM-34 molecular sieve to the organic template agent cR to the total organic solvent cS is 0.1-1: 1 to 10:1 to 10. Wherein all the organic solvents are the total amount of the first organic solvent cS in step 1) and the second organic solvent cS in step 2). The mass ratio of the first organic solvent cS in step 1) to the second organic solvent cS in step 2) is 1:0.1 to 1.
Further, in the step 1), the temperature of the first heat treatment is 40-90 ℃ and the time is 1-5 h; preferably, the temperature of the first heat treatment is 55-75 ℃ and the time is 2-4 h.
Further, in the step 2), the temperature of the second heat treatment is 40-90 ℃ and the time is 1-5 h; preferably, the temperature of the second heat treatment is 50-70 ℃ and the time is 2-3 h.
Further, in the step 2), the mass ratio of the silicon source to the SCM-34 molecular sieve is as follows: 0 to 10:1, preferably 0.1 to 10:1.
further, in the step 2), the silicon source is at least one of organic silicon, amorphous silicon dioxide, silica sol, white carbon black, silica gel, diatomite and water glass; preferably at least one of amorphous silica, silica sol and white carbon black.
Further, in step 3), the precursor P is preferably added to the mixture M in a stirred state for a period of 0.5 to 5 hours, preferably 2.5 to 4 hours.
Further, in step 4), the pretreatment conditions are as follows: stirring at 80-110 deg.c for 0.5-5 hr.
Further, in the step 4), the crystallization reaction conditions are as follows: crystallizing at 115-140 deg.c for 1-8 hr.
In a second aspect, the invention provides a SAPO-17 molecular sieve prepared by the method described above.
In a third aspect, the present invention provides the use of a SAPO-17 molecular sieve prepared by the method described above.
The SAPO-17 molecular sieve can be applied to the reaction of preparing hydrocarbon from methanol and the reaction of preparing olefin from synthesis gas.
Further, the reaction conditions for preparing hydrocarbon from methanol are as follows: methanol is used as raw material, the reaction temperature is 400-600 ℃, the reaction pressure is 0.01-10 MPa, and the weight airspeed of the methanol is 0.1-15 h -1 。
Further, the reaction conditions for preparing olefin from the synthesis gas are as follows: using synthesis gas as raw material H 2 Co=0.5 to 1:1, the reaction temperature is 200-400 ℃, the reaction pressure is 0.1-10 MPa, and the weight airspeed of the synthesis gas is 20-2000 h -1 。
When the SAPO-17 molecular sieve prepared by the invention is applied to the reaction of preparing hydrocarbon from methanol, the methanol conversion rate is 100% in the set evaluation condition range, the single-pass selectivity of ethylene and propylene can reach 84.5%, the selectivity ratio (ethylene/propylene) is in the range of 2.5-3.0, and the catalyst has good stability.
The SAPO-17 molecular sieve prepared by the invention is applied to the reaction process of preparing olefin from synthesis gas, the CO conversion rate can reach 51.7% at most in the set evaluation condition range, and C 2 -C 4 The selectivity of the olefin can reach 85.6%, and the selectivity ratio (ethylene/propylene) is in the range of 2.5-3.0.
Compared with the prior art, the invention has the following advantages:
the crystallization time for preparing the SAPO-17 molecular sieve is shorter, the total synthesis time of the SAPO-17 molecular sieve can be shortened to a certain extent, and the preparation can be performed at a lower temperature. Particularly, the invention adopts the self-developed SCM-34 molecular sieve to carry out crystal transformation to prepare the SAPO-17 molecular sieve for the first time, and the service performance of the SAPO-17 molecular sieve is obviously improved. The SAPO-17 molecular sieve synthesized by the method has excellent performances when used for industrial production of downstream products of methanol, industrial production of downstream products of synthesis gas and hydrocarbon cracking, such as high total yield of ethylene and propylene in hydrocarbon preparation reaction by methanol conversion, high selectivity ratio (ethylene/propylene), and C in hydrocarbon preparation reaction by synthesis gas 2 -C 4 The selectivity to olefins is high and the selectivity ratio (ethylene/propylene) is high.
Drawings
FIG. 1 is an XRD pattern for the SAPO-17 molecular sieve of example 1;
FIG. 2 is an SEM photograph of a SAPO-17 molecular sieve of example 1;
FIG. 3 is an XRD pattern of the SAPO-17 molecular sieve of comparative example 1;
FIG. 4 is an SEM photograph of the SAPO-17 molecular sieve of comparative example 1;
FIG. 5 is an XRD pattern for the SCM-34 molecular sieve of example 1.
Detailed Description
The present invention will be further described with reference to examples, but it should be understood that the scope of the present invention is not limited by the examples. In the present invention, percentages and percentages are by mass unless explicitly stated otherwise.
The methods of operation and handling involved in the present invention are conventional in the art, unless specifically stated otherwise.
The apparatus used in the present invention is a conventional apparatus in the art unless otherwise specified.
In the invention, the crystal phase of the product is measured by an X' Pert PRO X-ray powder diffractometer (XRD) of the Panac company of Netherlands, the working voltage is 40kV, the current is 40mA, and the scanning range is 5-50 degrees. The morphology of the product was photographed by a field emission scanning electron microscope (Fe-SEM) model S-4800 from HITACHI corporation of Japan.
[ example 1 ]
(I) Synthesis of SCM-34 molecular sieves
Taking 187.6g of aluminum nitrate to dissolve in 630.6mL of water, mixing to form a solution C, adding 74.9g of phosphoric acid (purity is equal to or higher than 85 wt.%), 1885.1g of tetrabutylammonium hydroxide (40 wt.% aqueous solution, MKSeal) and 2319.8g of 1- (3-aminopropyl) imidazole into the solution C, stirring for 2h, precipitating for 8h to obtain a solution C', slowly adding 6.1g of white carbon black (Allatin, S104573, > 99%), 99.9mL of N, N-dimethylformamide and 13.4mL of cyclohexanone into the solution C, stirring for 4h, and then heat-treating at 110 ℃ for 3h to form a uniform crystallization mixture, wherein Al is used 2 O 3 Aluminum source, in terms of SiO 2 Silicon source, in P 2 O 5 The mole ratio of the phosphorus source, the template agent and the solvent is as follows: al (Al) 2 O 3 ：SiO 2 ：P 2 O 5 : template agent R: solvent s=1: 0.1:1.3:20:100, template agent R1 (tetrabutylammonium hydroxide)/template agent R2 (1- (3-aminopropyl) imidazole) =0.17, solvent S1 (N, N-dimethylbutyramide)/solvent S2 (water)/solvent S3 (cyclohexanone) =1:72:0.1), crystallizing the crystallization mixture at 140 ℃ for 5d, filtering and washing the product, and drying at 120 ℃ for 4h to obtain the product SCM-34 (I). The X-ray diffraction pattern of the obtained SCM-34 (I) molecular sieve is shown in fig. 5. The X-ray diffraction pattern of the obtained SCM-34 (I) molecular sieve comprises X-ray diffraction peaks shown in the following table:
wherein, the incident ray of X-ray diffraction is Cu K alpha 1.
(II) Synthesis of SAPO-17 molecular sieves
At room temperature, 2.6g of piperazine (PIP) and 8.5g of 1, 4-Dioxane (DOA) are fully stirred, and then are subjected to heat treatment at 90 ℃ for 1.0h to obtain a precursor P 1 . 5.6g of SCM-34 molecular sieve prepared in the step (I) and 3.1g of white carbon black (SiO) are weighed 2 ) Mixing with 6.9g of 1, 4-dioxane solution, and heat treating at 40deg.C for 5 hr to obtain mixture M 1 . Precursor P 1 Adding the mixture M under intense stirring 1 Stirring for 2.5h continuously to form a crystallization mixture; stirring at 110deg.C for 0.5 hr, crystallizing at 140deg.C for 1 hr, filtering, washing, drying at 120deg.C for 4 hr, heating to 500deg.C, and calcining at constant temperature for 6 hr to obtain SAPO-17 molecular sieve, denoted STE-1, with XRD pattern shown in figure 1 and SEM pattern shown in figure 2.
[ example 2 ]
(I) Synthesis of SCM-34 molecular sieves
10.2g of aluminum isopropoxide (Al (iPr) was added 3 ) Dissolving in 23.3mL of water, mixing to form solution C, adding 4.3g of phosphoric acid (purity: not less than 85 wt.%), 147.6g of tetrabutylammonium hydroxide (40 wt.% aqueous solution, MKSeal) and 284.5g of 1- (3-aminopropyl) imidazole to the solution C, stirring for 5h, precipitating for 1h to obtain solution C ', slowly adding 7.5g of acidic silica sol (Ludox HS type, 40wt.% aqueous solution), 45.7mL of N, N-dimethylbutyramide and 1.4mL of cyclohexanone to the solution C', stirring for 2.5h, and then heat-treating at 100deg.C for 6h to form a uniform crystallization mixture, wherein Al is used as the solvent 2 O 3 Aluminum source, in terms of SiO 2 Silicon source, in P 2 O 5 The mole ratio of the phosphorus source, the template agent and the solvent is as follows: al (Al) 2 O 3 ：SiO 2 ：P 2 O 5 : template agent R: solvent s=1: 0.5:0.75:25:67.5 template R1 (tetraethylammonium hydroxide)/template R2 (1- (3-aminopropyl) imidazole) =0.1, solvent S1 (N, N-dimethylbutyryl)Amine)/solvent S2 (water)/solvent S3 (cyclohexanone) =1: 11:0.05; and (3) crystallizing the crystallization mixture at 140 ℃ for 4d, filtering and washing the product, and drying the product at 120 ℃ for 4h to obtain the product SCM-34 (II). Its X-ray diffraction line pattern resembles that of SCM-34 (I).
(II) Synthesis of SAPO-17 molecular sieves
666.7g of 1, 10-phenanthroline (1, 10-PIH), 731.3g of piperazine (PIP) and 1285.2g of 1, 2-cyclopentane epoxide (CPO) are stirred thoroughly at room temperature, and then heated at 40 ℃ for 5h to obtain a precursor P 2 . 239.8g of the SCM-34 molecular sieve prepared in the step (I) is weighed and mixed into 139.8g of 1, 2-cyclopentane epoxide (CPO) solution, and the mixture M is obtained by heat treatment at 90 ℃ for 1.0h 2 . Precursor P 2 Adding the mixture M under intense stirring 2 Stirring for 4.0h, and sealing and stirring at 80 ℃ for 5h; and then placing the mixture at 130 ℃ for crystallization for 2 hours, filtering and washing the product, drying the product at 100 ℃ for 6 hours, heating the product to 600 ℃, and roasting the product at constant temperature for 4 hours to obtain the product, namely STE-2. The XRD pattern is similar to that of FIG. 1 and the SEM pattern is similar to that of FIG. 2.
[ example 3 ]
(I) Synthesis of SCM-34 molecular sieves
9.4g of aluminum nitrate [ Al (NO) 3 ) 3 ·9H 2 O]Dissolving in 33.0mL deionized water, mixing to form solution C, adding 8.6g phosphoric acid (purity: 85 wt.%), 27g tetrabutylammonium hydroxide (40 wt.% aqueous solution, MKSeal) and 20.4g 1- (3-aminopropyl) imidazole into solution C, stirring for 0.5h, precipitating for 12h to obtain solution C ', slowly adding 0.8g white carbon black (Allatin, S104573, > 99%), 13.8mL N, N-dibutylformamide and 4.3mL cyclohexanone into the solution C', stirring for 3.5h, and heat treating at 90deg.C for 8h to form uniform crystallization mixture, wherein Al is used as the material 2 O 3 Aluminum source, in terms of SiO 2 Silicon source, in P 2 O 5 The mole ratio of the phosphorus source, the template agent and the solvent is as follows: al (Al) 2 O 3 ：SiO 2 ：P 2 O 5 : template agent R: solvent s=1:0.25:1.5:5:57.3, template R1 (tetrabutylammonium hydroxide)/template R2 (1- (3-aminopropyl) imidazole) =0.2, solvent S1 (N, N-dibutylnailAmide)/solvent S2 (water)/solvent S3 (cyclohexanone) =1: 31.7:0.5; and (3) crystallizing the crystallization mixture at 140 ℃ for 5 days, filtering and washing the product, and drying the product at 100 ℃ for 8 hours to obtain the product SCM-34 (III). Its X-ray diffraction line pattern resembles that of SCM-34 (I).
(II) Synthesis of SAPO-17 molecular sieves
At room temperature, 0.8g of cyclohexylamine (HCHA), 33.7g of piperazine (PIP), 5.5g of 1, 4-Dioxane (DOA) and 5.2g of Cyclohexanone (CHO) are stirred thoroughly, and then the mixture is subjected to heat treatment at 55 ℃ for 4.0h to obtain a precursor P 3 . 6.9g of the SCM-34 molecular sieve prepared in the step (I) is weighed and mixed into 5.0g of 1, 4-Dioxane (DOA) and 5.7g of Cyclohexanone (CHO) solution, and the mixture M is obtained by heat treatment at 70 ℃ for 2.0h 3 . Precursor P 3 Adding the mixture M under intense stirring 3 Stirring for 1h, and sealing and stirring at 100deg.C for 1h; and then crystallizing at 120 ℃ for 5 hours, filtering and washing the product, drying at 80 ℃ for 9 hours, heating to 400 ℃, and roasting at constant temperature for 8 hours to obtain the product, namely STE-3. The XRD pattern is similar to that of FIG. 1 and the SEM pattern is similar to that of FIG. 2.
[ example 4 ]
(I) Synthesis of SCM-34 molecular sieves
13.3g of aluminum sulfate [ Al ] is taken 2 (SO 4 ) 3 ·18H 2 O]Dissolving in 18.4mL of water, mixing to form solution C, adding 2.1g of phosphoric acid (purity: not less than 85 wt.%), 14.2g of tetrabutylammonium hydroxide (40 wt.% aqueous solution, MKSeal) and 16.1g of 1- (3-aminopropyl) imidazole into solution C, stirring for 3h, precipitating for 6h to obtain solution C ', slowly adding 1.2g of acidic silica sol (Ludox HS type, 40wt.% aqueous solution), 5.1mL of N, N-dimethylformamide and 0.9mL of cyclohexanone into the solution C', stirring for 4.5h, and heat-treating at 80deg.C for 12h to form a uniform crystallization mixture, wherein Al is used as the solvent 2 O 3 Aluminum source, in terms of SiO 2 Silicon source, in P 2 O 5 The mole ratio of the phosphorus source, the template agent and the solvent is as follows: al (Al) 2 O 3 ：SiO 2 ：P 2 O 5 : template agent R: solvent s=1: 0.4:0.9:10:80, template R1 (tetrabutylammonium hydroxide)/templateR2 (1- (3-aminopropyl) imidazole) =0.22, solvent S1 (N, N-dimethylbutyramide)/solvent S2 (water)/solvent S3 (cyclohexanone) =1: 48:0.3; and (3) crystallizing the crystallization mixture at 140 ℃ for 5 days, filtering and washing the product, and drying the product at 100 ℃ for 8 hours to obtain the product SCM-34 (IV). Its X-ray diffraction line pattern resembles that of SCM-34 (I).
(II) Synthesis of SAPO-17 molecular sieves
718.78g of cyclohexylamine (HCHA), 6252.5g of pyridine (PyD) and 16575.9g of 2-methyltetrahydrofuran (2-MeTHF) are stirred thoroughly at room temperature and then subjected to heat treatment at 75 ℃ for 2h to obtain a precursor P 4 . 1874.1g of SCM-34 molecular sieve prepared in step (I) and 26.1g of white carbon black (SiO) are weighed 2 ) Mixing with 5656.6g cyclohexanol solution, and heat treating at 50deg.C for 3 hr to obtain mixture M 4 . Precursor P 4 Adding the mixture M under intense stirring 4 Stirring for 4 hours, and then sealing and stirring for 4 hours at 90 ℃; and then crystallizing for 4 hours at 125 ℃, filtering and washing the product, drying for 8 hours at 80 ℃, then heating to 550 ℃, and roasting for 6 hours at constant temperature to obtain the product, which is named STE-4. The XRD pattern is similar to that of FIG. 1 and the SEM pattern is similar to that of FIG. 2.
[ example 5 ]
(I) Synthesis of SCM-34 molecular sieves
Dissolving 408.5g of aluminum isopropoxide in 1010.5mL of water, mixing to form a solution C, adding 253.6g of phosphoric acid (purity is equal to or higher than 85 wt.%), 16920.7g of tetrabutylammonium hydroxide (40 wt.% aqueous solution, MKSeal) and 21770.4g of 1- (3-aminopropyl) imidazole into the solution C, stirring for 3h, precipitating for 6h to obtain a solution C ', slowly adding 180.0g of white carbon black (Allatin, S104573, > 99%), 1811.5mL of N, N-dimethylbutyramide and 282.6mL of cyclohexanone into the solution C', stirring for 1.5h, and then heat-treating at 90 ℃ for 11h to form a uniform crystallization mixture, wherein Al is used 2 O 3 Aluminum source, in terms of SiO 2 Silicon source, in P 2 O 5 The mole ratio of the phosphorus source, the template agent and the solvent is as follows: al (Al) 2 O 3 ：SiO 2 ：P 2 O 5 : template agent R: solvent s=1:0.75:1.1:50:158.6, template R1 (tetrabutylammonium hydroxide)/template R2 (1- (3-amino group)Propyl) imidazole) =0.15, solvent S1 (N, N-dimethylbutyramide)/solvent S2 (water)/solvent S3 (cyclohexanone) =1: 53.9:0.22; and (3) crystallizing the crystallization mixture at 140 ℃ for 5 days, filtering and washing the product, and drying the product at 90 ℃ for 10 hours to obtain the product SCM-34 (V). Its X-ray diffraction line pattern resembles that of SCM-34 (I).
(II) Synthesis of SAPO-17 molecular sieves
At room temperature, 8.2g of 1, 10-phenanthroline (1, 10-PIH), 3.4g of cyclohexylamine (HCHA) and 6.5g of 1, 4-Dioxane (DOA) are fully stirred, and then the mixture is subjected to heat treatment at 60 ℃ for 3 hours to obtain a precursor P 5 . 2.5g of SCM-34 molecular sieve prepared in the step (I) and 25.0g of white carbon black (SiO) are weighed 2 ) Mixing with 61.4g of 1, 4-Dioxane (DOA) and heat-treating at 60deg.C for 2.5h to obtain a mixture M 5 . Precursor P 5 Adding the mixture M under intense stirring 5 Stirring for 2.5h, and sealing and stirring for 5h at 80 ℃; and then placing the mixture at 115 ℃ for crystallization for 8 hours, filtering and washing the product, drying the product at 110 ℃ for 5 hours, heating to 450 ℃, and roasting the product at constant temperature for 7 hours to obtain the product, namely STE-5. The XRD pattern is similar to that of FIG. 1 and the SEM pattern is similar to that of FIG. 2.
Examples 6 to 10
According to the method for preparing SCM-34 and the method for preparing SAPO-17 molecular sieves in example 5, the raw materials are shown in table 1, different proportions and conditions (see table 2) of reaction materials are controlled, and the SAPO-17 molecular sieves are respectively synthesized.
TABLE 1
TABLE 2
Comparative example 1
The SAPO-17 molecular sieve is prepared according to the synthesis method of the SAPO-17 molecular sieve disclosed in CN103922361A, and the specific steps are as follows: aluminum isopropoxide is used as an aluminum source, phosphoric acid is used as a phosphorus source, silica sol is used as a silicon source, cyclohexane is used as a template agent, 81g of aluminum isopropoxide is added into 48.9g of ultrapure water, 45.7g of phosphoric acid (85 wt.%) is added after uniform stirring, 11.5mL of cyclohexane is added into the mixed solution after stirring for 1h, and 30wt.% of SiO is added into the system after stirring and aging for 2h 2 After the solution is aged for several hours, the sol is put into a stainless steel reaction kettle with a polytetrafluoroethylene lining to crystallize for 120 hours at 200 ℃ to obtain a rod-shaped SAPO-17 molecular sieve with short and coarse morphology, the XRD pattern of the rod-shaped SAPO-17 molecular sieve is shown in figure 3, and the SEM pattern of the rod-shaped SAPO-17 molecular sieve is shown in figure 4
Comparative example 2
The synthesis of SAPO-17 molecular sieves described in the literature (Tianjin chemical industry, 2016, 30 (3): 17-19.) is specifically: aluminum isopropoxide is used as an aluminum source, phosphoric acid is used as a phosphorus source, silica sol is used as a silicon source, cyclohexylamine is used as a template agent, and the reaction ratio is 1Al 2 O 3 ∶1P 2 O 5 ∶0.3SiO 2 ∶1CHA∶1HF∶40H 2 O, fixing the scheme that the aluminum source dosage is 0.015mol, adding 3.06g of aluminum isopropoxide into 5.4g of deionized water, stirring uniformly, adding 1.7g of phosphoric acid (85 wt.%), stirring continuously for 1.5h, adding 0.7g of cyclohexylamine into the mixed solution, stirring and aging for 1.5h, adding 2.25g of silica sol (40 wt.%) into the reaction system, stirring continuously for several hours, and placing the sol into a stainless steel reaction kettle with a polytetrafluoroethylene lining for crystallization at 200 ℃ for 120h to obtain the SAPO-17 molecular sieve.
[ example 11 ]
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction from methanol
Taking STE-1 molecular sieve synthesized in example 1, roasting for 4 hours at 550 ℃, cooling to room temperature, tabletting, breaking, screening, and taking 12-20 mesh particles for standby. Methanol is used as raw material, a fixed bed reactor with the diameter of 15 mm is used, and the mass space velocity is 4.9h at 600 DEG C -1 Under the condition of 1.0MPa, the yield of ethylene and propylene reaches 78.7%, and the selectivity ratio (ethylene/propylene) =2.87 is obtainedThe technical effect is better.
[ example 12 ]
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction from methanol
Taking STE-4 molecular sieve synthesized in example 4, preparing catalyst by the catalyst preparation method in example 11, taking methanol as raw material, using a fixed bed reactor with diameter of 15 mm, and at 550 ℃ and mass space velocity of 15h -1 Under the condition of 10MPa, the yield of ethylene and propylene reaches 80.8 percent, and the selectivity ratio (ethylene/propylene) =2.76, thus obtaining better technical effect.
[ example 13 ]
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction by methanol conversion
The STE-7 molecular sieve synthesized in example 7 was taken, the catalyst prepared by the catalyst preparation method in example 11 was prepared by using methanol as a raw material, using a fixed bed reactor with a diameter of 15 mm, and using a mass space velocity of 7.1h at 474 ℃ -1 Under the condition of the pressure of 2.4MPa, the yield of ethylene and propylene reaches 84.5 percent, and the selectivity ratio (ethylene/propylene) =2.99, thereby obtaining better technical effect.
[ example 14 ]
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction by methanol conversion
Taking STE-8 molecular sieve synthesized in example 8, preparing catalyst by the catalyst preparation method in example 11, taking methanol as raw material, using a fixed bed reactor with diameter of 15 mm, and at 450 ℃ and mass space velocity of 1.9h -1 Under the condition of the pressure of 1.7MPa, the yield of ethylene and propylene reaches 81.7 percent, and the selectivity ratio (ethylene/propylene) =2.63, thereby obtaining better technical effect.
[ example 15 ]
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction by methanol conversion
The STE-9 molecular sieve synthesized in example 9 was taken, the catalyst prepared by the catalyst preparation method in example 11 was prepared by using methanol as a raw material, using a fixed bed reactor with a diameter of 15 mm, at 400℃and a mass space velocity of 0.1h -1 Evaluation of ethylene and propylene under the pressure of 0.01MPaThe yield of alkene reaches 78.6%, and the selectivity ratio (ethylene/propylene) =2.55, so that a better technical effect is obtained.
[ comparative example 3 ]
The SAPO-17 molecular sieve synthesized in comparative example 1 was selected, and a catalyst was prepared by the catalyst preparation method of example 11, and evaluated in the same manner as in example 15, so that the yields of ethylene and propylene were 33.3%, and the selectivity ratio (ethylene/propylene) =1.1.
[ comparative example 4 ]
The SAPO-17 molecular sieve synthesized in comparative example 2 was selected, and a catalyst was prepared by the catalyst preparation method of example 11, and evaluated in the same manner as in example 15, so that the yields of ethylene and propylene were 40.1%, and the selectivity ratio (ethylene/propylene) =1.2.
[ example 16 ]
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction of synthesis gas
Taking STE-1 molecular sieve synthesized in example 1, roasting for 6 hours at 550 ℃, tabletting, breaking, screening, taking particles with 20-40 meshes, and using a catalyst with the mass ratio of filler to ZnCrO x /STE＝1.0(ZnCrO x Representing a mixture of zinc oxide and chromium oxide, to produce an oxide-molecular sieve catalyst ready for use). The synthesis gas is used as raw material, a fixed bed reactor with the diameter of 15 mm is used, and the process conditions are as follows: the reaction temperature is 400 ℃, the pressure is 10MPa, and the space velocity is 2000h -1 Synthesis gas composition H 2 Co=0.5: 1, CO conversion was 41.9%, C 2＝ ～C 4＝ Selectivity was 66.9% and selectivity ratio (ethylene/propylene) =2.61.
[ example 17 ]
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction of synthesis gas
The catalyst was prepared by the catalyst preparation method of example 16 using the STE-6 molecular sieve synthesized in example 6. The process conditions are as follows: the reaction temperature is 375 ℃, the pressure is 7.5MPa, and the space velocity is 1000h -1 Synthesis gas composition H 2 Co=0.66: 1, CO conversion was 45.6%, C 2 ＝ ～C 4 ＝ Selectivity was 75.6% and selectivity ratio (ethylene/propylene) =2.66.
Example 18
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction of synthesis gas
The catalyst was prepared by the catalyst preparation method of example 16 using the STE-7 molecular sieves synthesized in example 7. The process conditions are as follows: the reaction temperature is 350 ℃, the pressure is 1.2MPa, and the space velocity is 500h -1 Synthesis gas composition H 2 Co=0.75: 1, CO conversion was 51.7%, C 2＝ ～C 4＝ Selectivity was 85.6% and selectivity ratio (ethylene/propylene) =2.98.
[ example 19 ]
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction of synthesis gas
The catalyst was prepared by the catalyst preparation method of example 16 using the STE-9 molecular sieves synthesized in example 9. The process conditions are as follows: the reaction temperature is 200 ℃, the pressure is 0.10MPa, and the space velocity is 20h -1 Synthesis gas composition H 2 Co=1: 1, CO conversion was 35.5%, C 2＝ ～C 4＝ Selectivity was 67.8% and selectivity ratio (ethylene/propylene) =2.54.
Comparative example 5
Application of SAPO-17 molecular sieve in hydrocarbon preparation reaction of synthesis gas
The SAPO-17 molecular sieve synthesized in comparative example 2 was selected, and a catalyst was prepared by the catalyst preparation method of example 17, and the conversion of CO was evaluated as in example 17 to be 22.3%, wherein C 2＝ ～C 4＝ Selectivity was 36.8% and selectivity ratio (ethylene/propylene) =1.21.

Claims (11)

1. A preparation method of a SAPO-17 molecular sieve comprises the following steps:
1) Mixing an organic template agent cR and a first organic solvent cS, and performing first heat treatment to obtain a precursor P;
2) Mixing an SCM-34 molecular sieve, a silicon source which is selectively added and a second organic solvent cS, and performing second heat treatment to obtain a mixed material M;
3) Mixing the precursor P obtained in the step 1) with the mixed material M obtained in the step 2) to form a crystallization mixture;
4) Pretreating the crystallization mixture obtained in the step 3), and then carrying out crystallization reaction to obtain the SAPO-17 molecular sieve;
the SCM-34 molecular sieve has the formula of Al 2 O 3 ：xSiO 2 ：yP 2 O 5 "the schematic chemical composition is shown, wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0.75 and less than or equal to 1.5; in XRD diffraction data of the SCM-34 molecular sieve, the 2 theta angle of the strongest peak in the range of 5-50 degrees is 7.59+/-0.2; the X-ray diffraction pattern of the SCM-34 molecular sieve comprises X-ray diffraction peaks shown in the following table:
2θ( o ) relative strength, [ (I/I) 0 )×100] 7.59±0.2 50-100 10.81±0.1 10-20 16.52±0.1 5-50 17.97±0.1 5-50 23.34±0.05 5-50 34.74±0.05 5-50
；
In the step 1), the organic template agent cR is at least one of 1, 10-phenanthroline, 2-bipyridine, 4-bipyridine, piperazine, cyclohexylamine and pyridine;
the mass ratio of the added SCM-34 molecular sieve to the organic template agent cR to the total organic solvent cS is 0.1-1: 1 to 10:1 to 10; wherein, the total organic solvent cS is the total amount of the first organic solvent cS in step 1) and the second organic solvent cS in step 2).
2. A method according to claim 1, characterized in that: in step 1) and step 2), the first organic solvent cS and the second organic solvent cS are each independently selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 2-cyclopentane, 1, 4-dioxane, cyclohexanone, cyclohexanol.
3. A method according to claim 1, characterized in that: the mass ratio of the first organic solvent cS in step 1) to the second organic solvent cS in step 2) is 1:0.1 to 1.
4. A method according to claim 1, characterized in that: in the step 1), the temperature of the first heat treatment is 40-90 ℃ and the time is 1-5 h.
5. The method of claim 4, wherein: in the step 1), the temperature of the first heat treatment is 55-75 ℃ and the time is 2-4 h.
6. A method according to claim 1, characterized in that: in the step 2), the temperature of the second heat treatment is 40-90 ℃ and the time is 1-5 h.
7. The method of claim 6, wherein: in the step 2), the temperature of the second heat treatment is 50-70 ℃ and the time is 2-3 h.
8. A method according to claim 1, characterized in that: in the step 2), the mass ratio of the silicon source to the SCM-34 molecular sieve is 0.1-10: 1.
9. the method according to claim 8, wherein: the silicon source is at least one of organic silicon, amorphous silicon dioxide, silica sol, white carbon black, silica gel, diatomite and water glass.
10. A method according to claim 1, characterized in that: in the step 4), the pretreatment conditions are as follows: stirring at 80-110 deg.c for 0.5-5 hr.
11. A method according to claim 1, characterized in that: in the step 4), the crystallization reaction conditions are as follows: crystallizing at 115-140 deg.c for 1-8 hr.
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