CN106044794B - A kind of preparation method of plate stratiform SAPO-34 molecular sieve - Google Patents

A kind of preparation method of plate stratiform SAPO-34 molecular sieve Download PDF

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CN106044794B
CN106044794B CN201610389108.3A CN201610389108A CN106044794B CN 106044794 B CN106044794 B CN 106044794B CN 201610389108 A CN201610389108 A CN 201610389108A CN 106044794 B CN106044794 B CN 106044794B
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gel
sapo
silicon source
template
stratiform
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CN106044794A (en
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王龙
明曰信
刘环昌
陈文勇
彭立
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SHANDONG QILU HUAXIN HIGH-TECHNOLOGY Co Ltd
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SHANDONG QILU HUAXIN HIGH-TECHNOLOGY Co Ltd
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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
    • 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

Abstract

The invention discloses a kind of preparation methods of plate stratiform SAPO-34 molecular sieve, this method obtains gel a by the way that phosphorus source, silicon source, template, silicon source and solvent to be uniformly mixed, stirring crystallization is promoted agent solution, then gained accelerator solution is added to phosphorus source, silicon source, silicon source, template and water are uniformly mixed and obtain in gel b, obtain plate stratiform SAPO-34 molecular sieve by hydrothermal crystallizing, centrifuge separation, washing, drying, roasting；The resulting SAPO-34 molecular sieve of Preparation Method of the present invention has plate stratiform pattern, crystallinity is high, it is shorter in section diffusion path when preparing the reaction of alkene for methanol, with excellent diffusion, it is able to extend the service life of catalyst, improves the yield of ethylene and propylene, on the one hand preparation method of the invention reduces the dosage of template, to reduce production cost, crystallization time is on the other hand shortened, reduces energy consumption.

Description

A kind of preparation method of plate stratiform SAPO-34 molecular sieve
Technical field
The present invention relates to the preparation method of SAPO molecular sieve, specifically a kind of preparation of plate stratiform SAPO-34 molecular sieve Method.
Background technique
SAPO-34 molecular sieve has suitable acid, lesser aperture and excellent hydrothermal stability, in methanol-to-olefins Excellent selectivity of light olefin and methanol conversion are shown in reaction, thus are seen as the best catalysis in MTO technique Agent, but current SAPO-34 molecular sieve is also easy to produce serious carbon distribution, blocking duct when MTO reacts, so as to cause catalyst Inactivation, research shows that partial size has longest service life and higher in MTO reaction less than 0.4 micron of SAPO-34 molecular sieve Diene selective, and almost without induction period, but the synthesis of SAPO-34 molecular sieve of the current partial size less than 0.4 micron Process is complicated, higher cost, and separation is difficult, and the requirement to equipment is high, is unfavorable for industrialized production.
Lamellated SAPO-34 molecular sieve is shorter in section diffusion path, and the low-carbon hydro carbons of generation can diffuse out rapidly It goes, alleviates the generation of carbon distribution, thus there is longer catalytic life and higher diene selective；Other two diffusion roads simultaneously Diameter is longer, has the characteristics that big crystal grain, is easily isolated, and is suitable for being mass produced, but Lamellated SAPO-34 molecule at present The synthetic method template of sieve is expensive, and the production cycle is long, is also easy to produce environmental pollution, therefore needs to develop one kind and be simple and efficient, pass through Help it is profitable, be suitable for industrial plate stratiform SAPO-34 molecular sieve.
Summary of the invention
To solve the above problems, the object of the present invention is to provide a kind of preparation methods of plate stratiform SAPO-34 molecular sieve.
The present invention to achieve the above object, is achieved through the following technical solutions:
A kind of preparation method of plate stratiform SAPO-34 molecular sieve, includes the following steps:
1. phosphorus source, silicon source, template, silicon source and solvent are uniformly mixed and obtain gel a, then gel a is added to instead It answers in kettle, is stirred crystallization 1 ~ 24 hour at 60 ~ 165 DEG C, temperature of reaction kettle is down to 20 ~ 30 DEG C after crystallization, is promoted Into agent solution；Solvent in the gel a: P2O5:Al2O3: template: SiO2Molar ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:1 ~ 3:0.02~1；The solvent is one or both of ethyl alcohol or water；
2. phosphorus source, silicon source, silicon source, template and water are uniformly mixed and obtain gel b, H in the gel b2O:P2O5: Al2O3: template: SiO2Molar ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:0.1 ~ 4:0.01 ~ 1；
3. by step, 1. resulting accelerator solution is added to step 2. in resulting gel b, gel c is obtained, by gained Gel c is added in crystallizing kettle, is warming up to 100 ~ 170 DEG C, is reacted 6 ~ 30 hours, is continuously heating to 170 ~ 220 DEG C, hydrothermal crystallizing 10 ~ 96 hours, obtain crystallization product；The quality of the accelerator solution accounts for the 0.1% ~ 20% of the quality of gel b；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecule Original powder is sieved, sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 500 ~ 600 DEG C of Muffle kiln roastings 4 ~ 6 hours, obtains plate layer Shape SAPO-34 molecular sieve.
Preferably, the silicon source of step 1. and 2. is boehmite, aluminium isopropoxide or aluminium hydroxide；Phosphorus source is phosphoric acid；Silicon Source is ethyl orthosilicate, silica solution or white carbon black；Template be tetraethyl ammonium hydroxide, isopropylamine, triethylamine, diethylamine, One or both of quinoline or n,N-diisopropylethylamine.
Preferably, 1. step stirs crystallization 20 hours at 95 DEG C.
Preferably, step 3. in accelerator solution quality account for gel b quality 10%.
Preferably, step 1. in solvent be water and ethyl alcohol be 1:1 according to molar ratio ratio mixing gained.
The preparation method of further preferred plate stratiform SAPO-34 molecular sieve, includes the following steps:
1. phosphorus source, silicon source, template, silicon source and solvent are uniformly mixed and obtain gel a, then gel a is added to instead It answers in kettle, is stirred crystallization 20 hours at 95 DEG C, temperature of reaction kettle is down to 25 DEG C after crystallization, is promoted agent solution； Solvent in the gel a: P2O5:Al2O3: template: SiO2Molar ratio be 80:1:1:2:0.5；Phosphorus source is phosphoric acid, institute Stating silicon source is aluminium hydroxide, and the template is tetraethyl ammonium hydroxide；Silicon source is ethyl orthosilicate, the solvent be ethyl alcohol and Water mixes gained according to the ratio that molar ratio is 1:1；
2. phosphorus source, silicon source, silicon source, template and water are uniformly mixed and obtain gel b, H in the gel b2O:P2O5: Al2O3: template: SiO2Molar ratio be 80:1:1:3:0.5；Phosphorus source is phosphoric acid, and source of aluminium is aluminium hydroxide, described Template is tetraethyl ammonium hydroxide；Silicon source is ethyl orthosilicate；
3. by step, 1. resulting accelerator solution is added to step 2. in resulting gel b, gel c is obtained, by gained Gel c is added in crystallizing kettle, is warming up to 150 DEG C, is reacted 20 hours, is continuously heating to 190 DEG C, hydrothermal crystallizing 20 hours, obtains To crystallization product；The quality of the accelerator solution accounts for the 10% of the quality of gel b；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecule Original powder is sieved, sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 550 DEG C of Muffle kiln roastings 5 hours, obtains plate stratiform SAPO-34 molecular sieve.
The present invention has the advantage that compared with prior art
There is plate stratiform pattern using the resulting SAPO-34 molecular sieve of preparation method of the present invention, crystallinity is high, is being used for first Alcohol prepare it is shorter in section diffusion path when the reaction of alkene, have excellent diffusion, be able to extend the service life of catalyst, Improve the yield of ethylene and propylene；Preparation method high income of the invention has big brilliant since other two diffusion paths are longer The characteristics of grain, is more easily than separation relative to nanoscale small particle size SAPO-34 molecular sieve, therefore is suitable for industrial big rule Mould production；Preparation method of the invention prepares plate stratiform SAPO-34 molecular sieve by the way that homemade accelerator solution is added, wherein promoting Not only there is the characteristic of crystal seed into agent solution, but also the growth of molecular sieve can be guided in crystallization process；In addition promotor is molten Liquid participates in the synthesis of molecular sieve directly as a kind of liquid charging stock, avoids separation of solid and liquid bring waste liquid and energy consumption is asked Topic；On the one hand preparation method of the invention reduces the dosage of template, to reduce production cost, on the other hand shorten crystalline substance Change the time, reduces energy consumption.
Detailed description of the invention
Fig. 1 is the XRD spectra of the resulting plate stratiform SAPO-34 molecular screen primary powder sample of embodiment 1 ~ 4；
Fig. 2 is that the SEM of the resulting plate stratiform SAPO-34 molecular screen primary powder sample of embodiment 1 schemes；
Fig. 3 is that the SEM of the resulting plate stratiform SAPO-34 molecular screen primary powder sample of embodiment 2 schemes；
Fig. 4 is that the SEM of the resulting plate stratiform SAPO-34 molecular screen primary powder sample of embodiment 3 schemes；
Fig. 5 is that the SEM of the resulting plate stratiform SAPO-34 molecular screen primary powder sample of embodiment 4 schemes.
Specific embodiment
The object of the present invention is to provide a kind of heat-resisting water-resistant type high strength polyurethane adhesive and preparation method thereof, by with Lower technical solution is realized:
A kind of preparation method of plate stratiform SAPO-34 molecular sieve, includes the following steps:
1. phosphorus source, silicon source, template, silicon source and solvent are uniformly mixed and obtain gel a, then gel a is added to instead It answers in kettle, is stirred crystallization 1 ~ 24 hour at 60 ~ 165 DEG C, temperature of reaction kettle is down to 20 ~ 30 DEG C after crystallization, is promoted Into agent solution；Solvent in the gel a: P2O5:Al2O3: template: SiO2Molar ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:1 ~ 3:0.02~1；The solvent is one or both of ethyl alcohol or water；
2. phosphorus source, silicon source, silicon source, template and water are uniformly mixed and obtain gel b, H in the gel b2O:P2O5: Al2O3: template: SiO2Molar ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:0.1 ~ 4:0.01 ~ 1；
3. by step, 1. resulting accelerator solution is added to step 2. in resulting gel b, gel c is obtained, by gained Gel c is added in crystallizing kettle, is warming up to 100 ~ 170 DEG C, is reacted 6 ~ 30 hours, is continuously heating to 170 ~ 220 DEG C, hydrothermal crystallizing 10 ~ 96 hours, obtain crystallization product；The quality of the accelerator solution accounts for the 0.1% ~ 20% of the quality of gel b；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecule Original powder is sieved, sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 500 ~ 600 DEG C of Muffle kiln roastings 4 ~ 6 hours, obtains plate layer Shape SAPO-34 molecular sieve.
Preferably, the silicon source of step 1. and 2. is boehmite, aluminium isopropoxide or aluminium hydroxide；Phosphorus source is phosphoric acid；Silicon Source is ethyl orthosilicate, silica solution or white carbon black；Template be tetraethyl ammonium hydroxide, isopropylamine, triethylamine, diethylamine, One or both of quinoline or n,N-diisopropylethylamine.
Preferably, 1. step stirs crystallization 20 hours at 95 DEG C.
Preferably, step 3. in accelerator solution quality account for gel b quality 10%.
Preferably, step 1. in solvent be water and ethyl alcohol be 1:1 according to molar ratio ratio mixing gained.
The preparation method of further preferred plate stratiform SAPO-34 molecular sieve, includes the following steps:
1. phosphorus source, silicon source, template, silicon source and solvent are uniformly mixed and obtain gel a, then gel a is added to instead It answers in kettle, is stirred crystallization 20 hours at 95 DEG C, temperature of reaction kettle is down to 25 DEG C after crystallization, is promoted agent solution； Solvent in the gel a: P2O5:Al2O3: template: SiO2Molar ratio be 80:1:1:2:0.5；Phosphorus source is phosphoric acid, institute Stating silicon source is aluminium hydroxide, and the template is tetraethyl ammonium hydroxide；Silicon source is ethyl orthosilicate, the solvent be ethyl alcohol and Water mixes gained according to the ratio that molar ratio is 1:1；
2. phosphorus source, silicon source, silicon source, template and water are uniformly mixed and obtain gel b, H in the gel b2O:P2O5: Al2O3: template: SiO2Molar ratio be 80:1:1:3:0.5；Phosphorus source is phosphoric acid, and source of aluminium is aluminium hydroxide, described Template is tetraethyl ammonium hydroxide；Silicon source is ethyl orthosilicate；
3. by step, 1. resulting accelerator solution is added to step 2. in resulting gel b, gel c is obtained, by gained Gel c is added in crystallizing kettle, is warming up to 150 DEG C, is reacted 20 hours, is continuously heating to 190 DEG C, hydrothermal crystallizing 20 hours, obtains To crystallization product；The quality of the accelerator solution accounts for the 10% of the quality of gel b；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecule Original powder is sieved, sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 550 DEG C of Muffle kiln roastings 5 hours, obtains plate stratiform SAPO-34 molecular sieve.
Below in conjunction with specific embodiment, the invention will be further described.
Al in boehmite used in the embodiment of the present invention 1 ~ 42O3Mass fraction 76%, the matter of tetraethyl ammonium hydroxide Measuring score is 35%, and the mass fraction of phosphoric acid is 85%, and the mass fraction of silica solution is 25%.
Embodiment 1
A kind of preparation method of plate stratiform SAPO-34 molecular sieve, includes the following steps:
1. by 11.5kg phosphoric acid, 6.7kg boehmite, 42kg tetraethyl ammonium hydroxide, 0.156kg silica solution and 36kg Water is uniformly mixed and obtains gel a, and then gel a is added in reaction kettle, is stirred crystallization 1 hour at 60 DEG C, crystallization terminates Temperature of reaction kettle is down to 20 ~ 30 DEG C afterwards, is promoted agent solution；
2. by 115kg phosphoric acid, 67kg boehmite, 4.2kg tetraethyl ammonium hydroxide, 0.78kg silica solution and 360kg Water is uniformly mixed and obtains gel b；
3. by 0.523kg step, 1. resulting accelerator solution is added to step 2. in resulting gel b, obtains gel c, Gained gel c is added in crystallizing kettle, is warming up to 100 DEG C, reacts 6 hours, is continuously heating to 170 DEG C, hydrothermal crystallizing 96 is small When, obtain crystallization product；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecule Original powder is sieved, sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 500 DEG C of Muffle kiln roastings 4 hours, obtains plate stratiform SAPO-34 molecular sieve, number S-1.
Embodiment 2
A kind of preparation method of plate stratiform SAPO-34 molecular sieve, includes the following steps:
1. by 54.78kg phosphoric acid, 97.92kg aluminium isopropoxide, 21.24kg isopropylamine, 9.36kg white carbon black, 496.8kg second Pure and mild 21.6kg water is uniformly mixed and obtains gel a, and then gel a is added in reaction kettle, and it is small that crystallization 24 is stirred at 165 DEG C When, temperature of reaction kettle is down to 30 DEG C after crystallization, is promoted agent solution；；
2. 456kg phosphoric acid, 816kg aluminium isopropoxide, 236kg isopropylamine, 78kg white carbon black and 1800kg water are uniformly mixed Obtain gel b；
3. by 663.6kg step, 1. resulting accelerator solution is added to step 2. in resulting gel b, obtains gel c, Gained gel c is added in crystallizing kettle, is warming up to 170 DEG C, reacts 30 hours, is continuously heating to 220 DEG C, hydrothermal crystallizing 96 is small When, obtain crystallization product；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecule Original powder is sieved, sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 600 DEG C of Muffle kiln roastings 6 hours, obtains plate stratiform SAPO-34 molecular sieve, number S-2.
Embodiment 3
A kind of preparation method of plate stratiform SAPO-34 molecular sieve, includes the following steps:
1. by 22.8kg phosphoric acid, 15.6kg aluminium hydroxide, 8.7kg morpholine, 7.3kg diethylamine, 8.32kg ethyl orthosilicate It is uniformly mixed with 230kg ethyl alcohol and obtains gel a, then gel a is added in reaction kettle, it is small that crystallization 10 is stirred at 95 DEG C When, temperature of reaction kettle is down to 24 DEG C after crystallization, is promoted agent solution；
2. by 136.9kg phosphoric acid, 124.8kg aluminium hydroxide, 130.5kg morpholine, 109.5kg diethylamine, the positive silicon of 20.8kg Acetoacetic ester and 720kg water, which are uniformly mixed, obtains gel b；
3. by 61.1kg step, 1. resulting accelerator solution is added to step 2. in resulting gel b, obtains gel c, Gained gel c is added in crystallizing kettle, is warming up to 150 DEG C, reacts 10 hours, is continuously heating to 180 DEG C, hydrothermal crystallizing 20 is small When, obtain crystallization product；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecule Original powder is sieved, sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 520 DEG C of Muffle kiln roastings 3 hours, obtains plate stratiform SAPO-34 molecular sieve, number S-3.
Embodiment 4
A kind of preparation method of plate stratiform SAPO-34 molecular sieve, includes the following steps:
1. by 22.8kg phosphoric acid, 15.6kg aluminium hydroxide, 84kg tetraethyl ammonium hydroxide, 10.4kg ethyl orthosilicate, 184kg ethyl alcohol and 72kg water, which are uniformly mixed, obtains gel a, and then gel a is added in reaction kettle, stirs crystallization at 95 DEG C 20 hours, temperature of reaction kettle is down to 25 DEG C after crystallization, is promoted agent solution；
2. by 228kg phosphoric acid, 156kg aluminium hydroxide, 1260kg tetraethyl ammonium hydroxide, 104kg ethyl orthosilicate and 1440kg water is uniformly mixed and obtains gel b；
3. by 233.5kg step, 1. resulting accelerator solution is added to step 2. in resulting gel b, obtains gel c, Gained gel c is added in crystallizing kettle, is warming up to 150 DEG C, reacts 20 hours, is continuously heating to 190 DEG C, hydrothermal crystallizing 20 is small When, obtain crystallization product；The quality of the accelerator solution accounts for the 10% of the quality of gel b；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecule Original powder is sieved, sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 550 DEG C of Muffle kiln roastings 5 hours, obtains plate stratiform SAPO-34 molecular sieve, number S-4.
The XRD spectra of the resulting plate stratiform SAPO-34 molecular screen primary powder sample of embodiment 1 ~ 4 is as shown in Figure 1, SEM picture As shown in Fig. 2 ~ 5.By the result of Fig. 1 ~ 5 may indicate that the resulting SAPO-34 molecular sieve of embodiment 1 ~ 4 be pure phase, plate stratiform, Structure is CHA topological structure, and particle size is each about 1.8 × 1.8 × 0.4 μm.
The resulting plate stratiform SAPO-34 molecular sieve of embodiment 1 ~ 4 carries out tabletting, is crushed to 40 ~ 60 mesh.1.0g sample is taken to fill Enter fixed bed reactors, carries out MTO performance test.Test condition are as follows: catalyst activates 1 hour at 500 DEG C, is cooled to 450 ℃.Methanol charging is loaded by nitrogen, stream of nitrogen gas 30ml/min, and methanol water content is 60%, air speed 1.5h-1.Gas phase produces Object is detected by the glad GC-950 type gas chromatograph (fid detector) in sea.Chromatographic column be PLOT Q capillary column (30m × 0.32mm × 10 μm).Analysis the results are shown in Table 1.As can be seen from Table 1, the resulting plate stratiform SAPO-34 molecular sieve of embodiment 1 ~ 4 All have longer service life (methanol conversion be greater than 99.9%) and higher ethylene, propene yield, and ethylene and propylene Selectivity reaches 94% or more.
Table 1: the MTO reaction test result of sample
。

Claims (3)

1. a kind of preparation method of plate stratiform SAPO-34 molecular sieve, characterized by the following steps:
1. phosphorus source, silicon source, template, silicon source and solvent are uniformly mixed and obtain gel a, gel a is then added to reaction kettle In, it is stirred crystallization 1 ~ 24 hour at 60 ~ 165 DEG C, temperature of reaction kettle is down to 20 ~ 30 DEG C after crystallization, is promoted agent Solution；Solvent in the gel a: P2O5:Al2O3: template: SiO2Molar ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:1 ~ 3: 0.02~1；The solvent is the ratio mixing gained that water and ethyl alcohol are 1:1 according to molar ratio；Silicon source is boehmite, isopropyl Aluminium alcoholates or aluminium hydroxide；Phosphorus source is phosphoric acid；Silicon source is ethyl orthosilicate, silica solution or white carbon black；Template is tetraethyl hydrogen-oxygen Change one or both of ammonium, isopropylamine, triethylamine, diethylamine, morpholine or n,N-diisopropylethylamine；
2. phosphorus source, silicon source, silicon source, template and water are uniformly mixed and obtain gel b, H in the gel b2O:P2O5:Al2O3: mould Plate agent: SiO2Molar ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:0.1 ~ 4:0.01 ~ 1；Silicon source is boehmite, aluminium isopropoxide Or aluminium hydroxide；Phosphorus source is phosphoric acid；Silicon source is ethyl orthosilicate, silica solution or white carbon black；Template be tetraethyl ammonium hydroxide, One or both of isopropylamine, triethylamine, diethylamine, morpholine or n,N-diisopropylethylamine；
3. by step, 1. resulting accelerator solution is added to step 2. in resulting gel b, gel c is obtained, by gained gel c It is added in crystallizing kettle, is warming up to 100 ~ 170 DEG C, react 6 ~ 30 hours, be continuously heating to 170 ~ 220 DEG C, hydrothermal crystallizing 10 ~ 96 Hour, obtain crystallization product；The quality of the accelerator solution accounts for the 10% of the quality of gel b；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecular screen primary Sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 500 ~ 600 DEG C of Muffle kiln roastings 4 ~ 6 hours, obtains plate stratiform by powder SAPO-34 molecular sieve.
2. the preparation method of plate stratiform SAPO-34 molecular sieve according to claim 1, it is characterised in that: step is 1. 95 It is stirred crystallization 20 hours at DEG C.
3. the preparation method of plate stratiform SAPO-34 molecular sieve according to claim 1, it is characterised in that: including walking as follows It is rapid:
1. phosphorus source, silicon source, template, silicon source and solvent are uniformly mixed and obtain gel a, gel a is then added to reaction kettle In, it is stirred crystallization 20 hours at 95 DEG C, temperature of reaction kettle is down to 25 DEG C after crystallization, is promoted agent solution；It is described Solvent in gel a: P2O5:Al2O3: template: SiO2Molar ratio be 80:1:1:2:0.5；Phosphorus source is phosphoric acid, the aluminium Source is aluminium hydroxide, and the template is tetraethyl ammonium hydroxide；Silicon source is ethyl orthosilicate, and the solvent is that second alcohol and water is pressed Gained is mixed according to the ratio that molar ratio is 1:1；
2. phosphorus source, silicon source, silicon source, template and water are uniformly mixed and obtain gel b, H in the gel b2O:P2O5:Al2O3: mould Plate agent: SiO2Molar ratio be 80:1:1:3:0.5；Phosphorus source is phosphoric acid, and source of aluminium is aluminium hydroxide, the template For tetraethyl ammonium hydroxide；Silicon source is ethyl orthosilicate；
3. by step, 1. resulting accelerator solution is added to step 2. in resulting gel b, gel c is obtained, by gained gel c It is added in crystallizing kettle, is warming up to 150 DEG C, react 20 hours, be continuously heating to 190 DEG C, hydrothermal crystallizing 20 hours, obtain crystallization Product；The quality of the accelerator solution accounts for the 10% of the quality of gel b；
4. by step, 3. gained crystallization product is centrifuged, and filter cake is washed, is dried to obtain plate stratiform SAPO-34 molecular screen primary Sheets thus obtained stratiform SAPO-34 molecular screen primary powder is placed in 550 DEG C of Muffle kiln roastings 5 hours, obtains plate stratiform SAPO-34 by powder Molecular sieve.
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CN108706609B (en) * 2018-06-07 2021-07-30 深圳科冠华太新材料技术有限公司 Preparation method of nano SAPO-34molecular sieve
CN111013650A (en) * 2019-12-25 2020-04-17 山东江岳科技开发股份有限公司 SAPO-34 molecular sieve thin-layer catalyst and preparation method thereof
CN114426295B (en) * 2020-09-27 2023-08-29 中国石油化工股份有限公司 AFX type molecular sieve and synthetic method and application thereof

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CN104445266A (en) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 Preparation method of small-grain-size SAPO-34 molecular sieve

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