CN102001682A - Method for synthesizing heteroatom substituted MeAPO-31 molecular sieve by microwave heating - Google Patents
Method for synthesizing heteroatom substituted MeAPO-31 molecular sieve by microwave heating Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a heteroatom substituted MeAPO-31 molecular sieve by microwave heating, relating to a preparation method of a MeAPO-31 molecular sieve. The invention aims to solve the technical problems that the traditional method for preparing the MeAPO-31 molecular sieve has long crystallization time, easy generation of mixed crystals in products, limited type and quantity of the heteroatom introduced into a frameworkd, the narrow adjustable range of the produced acid sites and the like. The method comprises the following steps of: firstly, preparing gel by using phosphoric acid, water, di-n-butylamine, aluminum isopropoxide (or boehmite) and metal salt; heating with microwaves; and crystallizing, then centrifugally filtering, washing, drying and roasting to obtain the MeAPO-31 molecular sieve. Compared with the traditional hydrothermal process, the method disclosed in the invention obviously shortens the crystallization time of the molecular sieve and does not generate mixed crystals. The MeAPO-31 molecular sieve prepared with the method can be used as catalysts in the fields of petrochemical industry, fine chemical industry and the like.
Description
Technical field
The present invention relates to the preparation method of MeAPO-31 molecular sieve.
Background technology
AlPO-31 is by AlO
4With PO
4The aluminium phosphate molecular sieve with ATO type topological framework that tetrahedron alternately rearranges, the skeleton charge balance does not have acidic site.Metal heteroatoms such as Mg, Co, Zn, Ti, Mn, Fe, V are introduced the aluminium phosphate molecular sieve skeleton make the MeAPO-31 molecular sieve that heteroatoms replaces partly to replace Al or P, make the skeleton of aluminium phosphate molecular sieve that tradable electric charge arranged, can be used as and have gentle tart molecular sieve catalyst.(SAPO-31) compares with the silicoaluminophosphamolecular molecular sieves with identical topological framework, the MeAPO-31 molecular sieve of only introducing heteroatomss formation such as a spot of Mg, Co in the AlPO-31 framework of molecular sieve can produce abundant active sites, overcome in the SAPO-31 sieve synthesis procedure because of introducing a large amount of Si atoms and could form enough acidic sites and easily produce drawbacks such as SAPO-5 and SAPO-11 molecular sieve stray crystal, and can realize meticulous modulation to the acidity of MeAPO-31 molecular sieve easily and flexibly by changing heteroatoms kind and the quantity introduced.Because the synthesis condition of MeAPO-31 is simple and easy to do, has milder and acidity that can meticulous modulation than SAPO-31, MeAPO-31 has metal active center and acid site when supporting the precious metal preparation dual-function catalyst has higher selectivity to isoparaffin in the isomerization reaction of normal paraffin shortening, can be used for preparing the catalyzer of eco-friendly gasoline alkylate, low-freezing diesel oil and efficient lubricant oil.The preparation method of existing MeAPO-31 molecular sieve is a synthetic under hydrothermal condition, and adopting di-n-propylamine usually is template, with aluminium source, phosphorus source, metal-salt, water and a little HF or HNO
3Mix Deng mineral acid, join in the autoclave, airtight post-heating to 150 ℃～200 ℃, crystallization is 3～5 days under autogenous pressure.This method crystallization time is long, and because use can cause SAPO-5, the di-n-propylamine that nearly ten kinds of molecular sieves such as SAPO-11 and SAPO-41 form is a template, be prone to stray crystal in the crystallization product, and limited as the value volume and range of product of the atoms metal on the heteroatoms introducing framework of molecular sieve, limited the synthetic and application of MeAPO-31 molecular sieve.
In sum, technical problems such as being prone to stray crystal in long, the product of the method crystallization time of existing preparation MeAPO-31 molecular sieve, introducing heteroatoms kind in the skeleton and limited amount, the acidic site variable range of generation is narrow.
Summary of the invention
Technical problems such as the present invention will solve that the method crystallization time of existing preparation MeAPO-31 molecular sieve is long, be prone to stray crystal in the product, introduce heteroatoms kind in the skeleton and limited amount, the acidic site variable range of generation is narrow, and provide the synthetic heteroatoms of a kind of microwave heating to replace the method for MeAPO-31 (Me is meant heteroatomss such as Mg, Co, Mn, Fe, Cr, Ti, Cu, Zn, V) molecular sieve.
The method of the synthetic MeAPO-31 molecular sieve of microwave heating is carried out according to the following steps among the present invention: one, strong phosphoric acid is added in the entry, stir 5min～10min, continue to stir 10～30min after adding Di-n-Butyl Amine again, continue to stir 1h～8h after adding metal-salt and aluminium salt again, obtain gel, the mass ratio of wherein said strong phosphoric acid and water is 1: 2.5～4, the mass ratio of strong phosphoric acid and Di-n-Butyl Amine is 1: 0.4～1.2, the mass ratio of strong phosphoric acid and metal-salt is 1: 0.04～1.0, described aluminium salt is aluminum isopropylate or pseudo-boehmite, the mass ratio of strong phosphoric acid and aluminum isopropylate is 1.2～2, and the mass ratio of strong phosphoric acid and pseudo-boehmite is 0.2～1.2; Two, the gel that step 1 is obtained places reactor, use microwave as heating source, the power of described microwave is 500W～700W, crystallization 0.5h～3h under 130～190 ℃ condition, be cooled to room temperature, obtain the MeAPO-31 molecular sieve after centrifuging then, washing, drying, the roasting; Metal-salt described in the step 1 is magnesium salts, cobalt salt, manganese salt, molysite, chromic salts, titanium salt, mantoquita, zinc salt or vanadic salts.
The present invention adopts microwave to heat, and just obtains the pure phase MeAPO-31 molecular sieve of high-crystallinity during crystallization 0.5h under microwave heating condition～3h, does not have MeAPO-5, stray crystals such as MeAPO-11 and MeAPO-41; Crystallization time shortens dramatically, and only is 1/20～1/40 of traditional hydrothermal method.Can adopt the Di-n-Butyl Amine and the pseudo-boehmite of industrial level respectively is organic formwork agent and aluminium source, and the cost of synthetic MeAPO-31 molecular sieve is reduced significantly.Adopt this patent method can synthesize Me
XO
Y/ P
2O
5Mol ratio in 0.01～0.1 scope, change, have different tart MeAPO-31 molecular sieves, have broad application prospects in fields such as petrochemical complex, fine chemistry industries as eco-friendly an acidic catalyst.
Description of drawings
Fig. 1 is the XRD spectra of the sieve sample MgAPO-31 (A) of embodiment 17 preparations; Fig. 2 is the SEM photo of the sieve sample MgAPO-31 (A) of embodiment 17 preparations; Fig. 3 is the XRD spectra of the sieve sample MgAPO-31 (N) of embodiment 18 preparations; Fig. 4 is the SEM photo of the sieve sample MgAPO-31 (N) of embodiment 18 preparations; Fig. 5 is the XRD spectra of the sieve sample MgAPO-31 (PA) of embodiment 19 preparations; Fig. 6 is the SEM photo of the sieve sample MgAPO-31 (PA) of embodiment 19 preparations; Fig. 7 is the XRD spectra of the sieve sample CoAPO-31 (S) of embodiment 20 preparations; Fig. 8 is the SEM photo of the sieve sample CoAPO-31 (S) of embodiment 20 preparations.Fig. 9 is the XRD spectra of the sieve sample CoAPO-31 (N) of embodiment 21 preparations; Figure 10 is the SEM photo of the sieve sample CoAPO-31 (N) of embodiment 21 preparations.
Embodiment
Embodiment one: the method for the synthetic MeAPO-31 molecular sieve of microwave heating is carried out according to the following steps in the present embodiment: one, strong phosphoric acid is added in the entry, stir 5min～10min, continue to stir 10～30min after adding Di-n-Butyl Amine again, continue to stir 1h～8h after adding metal-salt and aluminium salt again, obtain gel, the mass ratio of wherein said strong phosphoric acid and water is 1: 2.5～4, the mass ratio of strong phosphoric acid and Di-n-Butyl Amine is 1: 0.4～1.2, the mass ratio of strong phosphoric acid and metal-salt is 1: 0.04～1.0, described aluminium salt is aluminum isopropylate or pseudo-boehmite, the mass ratio of strong phosphoric acid and aluminum isopropylate is 1.2～2, and the mass ratio of strong phosphoric acid and pseudo-boehmite is 0.2～1.2; Two, the gel that step 1 is obtained places reactor, use microwave as heating source, the power of described microwave is 500W～700W, crystallization 0.5h～3h under 130～190 ℃ condition, be cooled to room temperature, obtain the MeAPO-31 molecular sieve after centrifuging then, washing, drying, the roasting; Metal-salt described in the step 1 is magnesium salts, cobalt salt, manganese salt, molysite, chromic salts, titanium salt, mantoquita, zinc salt or vanadic salts.
Quality percentage composition 〉=85% of present embodiment strong phosphoric acid.
The organic formwork agent that present embodiment adopts is a Di-n-Butyl Amine, adopting microwave to heat can make crystallization time shorten dramatically, crystallization time only is 1/20～1/40 of traditional hydrothermal method, crystallization 0.5h～3h just obtains the pure phase MeAPO-31 molecular sieve of high-crystallinity under microwave heating condition, do not have MeAPO-5 in the product, stray crystals such as MeAPO-11 and MeAPO-41 occur.
Embodiment two: what present embodiment and embodiment one were different is: the described magnesium salts of step 1 is magnesium acetate or magnesium nitrate, described cobalt salt is rose vitriol, Xiao Suangu or Cobaltous diacetate, described manganese salt is manganese acetate or manganous sulfate, described molysite is iron nitrate or ferric sulfate, described chromic salts is chromium nitrate or chromium acetate, and described titanium salt is titanium chloride or tetrabutyl titanate, and described mantoquita is cupric nitrate, copper sulfate or cupric chloride, described zinc salt is zinc acetate or zinc sulfate, and described vanadic salts is an ammonium vanadate.Other step is identical with embodiment one with parameter.
Embodiment three: what present embodiment was different with embodiment one or two is: the described stirring velocity of step 1 is 200r/min.Other step is identical with embodiment one or two with parameter.
Embodiment four: what present embodiment was different with one of embodiment one to three is: the mass ratio of described strong phosphoric acid of step 1 and water is 1: 2.7～3.8.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what present embodiment was different with one of embodiment one to four is: the mass ratio of described strong phosphoric acid of step 1 and Di-n-Butyl Amine is 1: 0.7～0.9.Other step is identical with one of embodiment one to four with parameter.
Embodiment six: what present embodiment was different with one of embodiment one to five is: the mass ratio of described strong phosphoric acid of step 1 and metal-salt is 0.06～0.8.Other step is identical with one of embodiment one to five with parameter.
Embodiment seven: what present embodiment was different with one of embodiment one to six is: the mass ratio of described strong phosphoric acid of step 1 and aluminum isopropylate is 1.6～1.9.Other step is identical with one of embodiment one to six with parameter.
Embodiment eight: what present embodiment was different with one of embodiment one to seven is: the mass ratio of described strong phosphoric acid of step 1 and pseudo-boehmite is 0.4～1.0.Other step is identical with one of embodiment one to seven with parameter.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is: the described crystallization temperature of step 2 is 140～180 ℃, and crystallization time is 1h～2.5h.Other step is identical with one of embodiment one to eight with parameter.
Embodiment ten: what present embodiment was different with one of embodiment one to eight is: the described crystallization temperature of step 2 is 175 ℃, and crystallization time is 2h.Other step is identical with one of embodiment one to eight with parameter.
Embodiment 11: what present embodiment was different with one of embodiment one to ten is: drying temperature described in the step 2 is 100 ℃～120 ℃, and be 12h～24h time of drying.Other step is identical with one of embodiment one to ten with parameter.
Embodiment 12: what present embodiment was different with one of embodiment one to ten is: drying temperature described in the step 2 is 110 ℃, and be 15h time of drying.Other step is identical with one of embodiment one to ten with parameter.
Embodiment 13: what present embodiment was different with one of embodiment one to 12 is: the maturing temperature described in the step 2 is 500～600 ℃, and roasting time is 2h～6h.Other step is identical with one of embodiment one to 12 with parameter.
Embodiment 14: what present embodiment was different with one of embodiment one to 12 is: the maturing temperature described in the step 2 is 550 ℃, and roasting time is 4h.Other step is identical with one of embodiment one to 12 with parameter.
Embodiment 15: what present embodiment was different with one of embodiment one to 14 is: the power of the described microwave of step 2 is 550W～650W.Other step is identical with one of embodiment one to 14 with parameter.
Embodiment 16: what present embodiment was different with one of embodiment one to 14 is: the power of the described microwave of step 2 is 600W.Other step is identical with one of embodiment one to 14 with parameter.
Embodiment 17: the method for the synthetic MgAPO-31 molecular sieve of microwave heating is carried out according to the following steps in the present embodiment: one, strong phosphoric acid (mass concentration is 85%) is added in the entry, stir 10min, continue to stir 15min after adding Di-n-Butyl Amine again, continue to stir 100min after adding magnesium acetate and aluminum isopropylate again, obtain gel, the mass ratio of wherein said strong phosphoric acid and water is 1: 3, the mass ratio of strong phosphoric acid and Di-n-Butyl Amine is 1: 0.8, the mass ratio of strong phosphoric acid and aluminum isopropylate is 1: 1.78, and the mass ratio of strong phosphoric acid and magnesium acetate is 1: 0.047; Two, the gel that step 1 is obtained places reactor, use microwave as heating source, the power of described microwave is 600W, crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging, extremely neutral with deionized water wash, dry 15h under 110 ℃ obtains the MgAPO-31 molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as MgAPO-31 (A).
The XRD figure spectrum of the sieve sample MgAPO-31 (A) of present embodiment preparation and SEM photo are respectively as depicted in figs. 1 and 2.From Fig. 1 as seen, be 8.5 ° at 2 θ, 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework have obtained the pure phase MgAPO-31 molecular sieve of high-crystallinity.As seen from Figure 2, present embodiment synthetic MgAPO-31 molecular sieve crystal is that diameter is the nanometer rod of 50nm, exists with the pencil aggregate form.
Embodiment 18: the method for the synthetic MgAPO-31 molecular sieve of a kind of microwave heating of present embodiment is carried out according to the following steps: one, strong phosphoric acid (mass concentration is 85%) is added in the entry, stir 10min, continue to stir 15min after adding Di-n-Butyl Amine again, continue to stir 100min after adding magnesium nitrate and aluminum isopropylate again, obtain gel, the mass ratio of wherein said strong phosphoric acid and water is 1: 3, the mass ratio of strong phosphoric acid and Di-n-Butyl Amine is 1: 0.8, the mass ratio of strong phosphoric acid and aluminum isopropylate is 1: 1.78, and the mass ratio of strong phosphoric acid and magnesium nitrate is 1: 0.053; Two, the gel that step 1 is obtained places reactor, use microwave as heating source, the power of described microwave is 600W, crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging, extremely neutral with deionized water wash, dry 15h under 110 ℃ obtains the MgAPO-31 molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as MgAPO-31 (N).
The XRD figure of the sieve sample MgAPO-31 (N) of present embodiment preparation is composed as shown in Figure 3, and the SEM photo as shown in Figure 4.As can be seen from Figure 3, be 8.5 ° at 2 θ, 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework do not have other stray crystal; As shown in Figure 4, the MgAPO-31 crystal grain that makes of present embodiment exists with cage shape aggregate form.
Embodiment 19: the method for the synthetic MgAPO-31 molecular sieve of a kind of microwave heating of present embodiment is carried out according to the following steps: one, strong phosphoric acid (mass concentration is 85%) is added in the entry, stir 10min, continue to stir 15min after adding Di-n-Butyl Amine again, continue to stir 240min after adding magnesium acetate and pseudo-boehmite again, obtain gel, the mass ratio of wherein said strong phosphoric acid and water is 1: 3, the mass ratio of strong phosphoric acid and Di-n-Butyl Amine is 1: 0.8, the mass ratio of strong phosphoric acid and pseudo-boehmite is 1: 0.6, and the mass ratio of strong phosphoric acid and magnesium acetate is 1: 0.047; Two, the gel that step 1 is obtained places reactor, use microwave as heating source, the power of described microwave is 600W, crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging, extremely neutral with deionized water wash, dry 15h under 110 ℃ obtains the MgAPO-31 molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as MgAPO-31 (PA).
The XRD figure spectrum of the sieve sample MgAPO-31 (PA) of present embodiment preparation and SEM photo are respectively as shown in Figure 5 and Figure 6.As can be seen from Figure 5, be 8.5 ° at 2 θ, 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework do not have other stray crystal.As shown in Figure 6, the MgAPO-31 crystal grain that makes of present embodiment is capsule shape.
Embodiment 20: the method for the synthetic CoAPO-31 molecular sieve of a kind of microwave heating of present embodiment is carried out according to the following steps: one, strong phosphoric acid (mass concentration is 85%) is added in the entry, stir 10min, continue to stir 15min after adding Di-n-Butyl Amine again, continue to stir 100min after adding rose vitriol and aluminum isopropylate stone again, obtain gel, the mass ratio of wherein said strong phosphoric acid and water is 1: 3, the mass ratio of strong phosphoric acid and Di-n-Butyl Amine is 1: 0.8, the mass ratio of strong phosphoric acid and aluminum isopropylate is 1: 1.78, and the mass ratio of strong phosphoric acid and rose vitriol is 1: 0.061; Two, the gel that step 1 is obtained places reactor, use microwave as heating source, the power of described microwave is 600W, crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging, extremely neutral with deionized water wash, dry 15h under 110 ℃ obtains the CoAPO-31 molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as CoAPO-31 (S).
The XRD figure spectrum of the sieve sample CoAPO-31 (S) of present embodiment preparation as shown in Figure 7, the SEM photo as shown in Figure 8, as can be seen from Figure 7, at 2 θ is 8.5 °, 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework do not have other stray crystal; As shown in Figure 8, the CoAPO-31 molecular sieve crystal that present embodiment makes is that diameter is the nanometer rod of 50nm, the crystal that exists with the pencil aggregate form.
Embodiment 21: the method for the synthetic CoAPO-31 molecular sieve of a kind of microwave heating of present embodiment is carried out according to the following steps: one, strong phosphoric acid (mass concentration is 85%) is added in the entry, stir 10min, continue to stir 15min after adding Di-n-Butyl Amine again, continue to stir 100min after adding Xiao Suangu and aluminum isopropylate stone again, obtain gel, the mass ratio of wherein said strong phosphoric acid and water is 1: 3, the mass ratio of strong phosphoric acid and Di-n-Butyl Amine is 1: 0.8, the mass ratio of strong phosphoric acid and aluminum isopropylate is 1: 1.78, and the mass ratio of strong phosphoric acid and Xiao Suangu is 1: 127; Two, the gel that step 1 is obtained places reactor, use microwave as heating source, the power of described microwave is 600W, crystallization 2h is cooled to room temperature under 175 ℃ condition, then centrifuging, extremely neutral with deionized water wash, dry 15h under 110 ℃ obtains CoAPO-31 (N) molecular sieve behind roasting 4h under 550 ℃ of conditions, sample is designated as CoAPO-31 (N).
The XRD figure of the sieve sample CoAPO-31 (N) of present embodiment preparation is composed as shown in Figure 9, and the SEM photo as shown in figure 10.As can be seen from Figure 9, be 8.5 ° at 2 θ, 20.0 °, 22.0 ° and 22.5 ° of characteristic diffraction peaks of locating all to have the ATO topological framework do not have other stray crystal; As shown in Figure 10, the CoAPO-31 molecular sieve crystal diameter that present embodiment makes is the nanometer rod of 50nm, exists with the pencil aggregate form.Just obtain the pure phase CoAPO-31 molecular sieve of high-crystallinity under microwave heating condition during crystallization 2h, crystallization time is 1/20 of traditional hydrothermal method only, and crystallization time shortens dramatically; The organic formwork agent that adopts is the Di-n-Butyl Amine of industrial level, and the cost of synthetic CoAPO-31 molecular sieve is further reduced.
Claims (10)
1. the method that heteroatoms replaces the MeAPO-31 molecular sieve is synthesized in a microwave heating, the method that it is characterized in that the synthetic MeAPO-31 molecular sieve of microwave heating is carried out according to the following steps: one, strong phosphoric acid is added in the entry, stir 5min～10min, continue to stir 10～30min after adding Di-n-Butyl Amine again, continue to stir 1h～8h after adding metal-salt and aluminium salt again, obtain gel, the mass ratio of wherein said strong phosphoric acid and water is 1: 2.5～4, the mass ratio of strong phosphoric acid and Di-n-Butyl Amine is 1: 0.4～1.2, the mass ratio of strong phosphoric acid and metal-salt is 1: 0.04～1.0, described aluminium salt is aluminum isopropylate or pseudo-boehmite, the mass ratio of strong phosphoric acid and aluminum isopropylate is 1.2～2, and the mass ratio of strong phosphoric acid and pseudo-boehmite is 0.2～1.2; Two, the gel that step 1 is obtained places reactor, use microwave as heating source, the power of described microwave is 500W～700W, crystallization 0.5h～3h under 130～190 ℃ condition, be cooled to room temperature, obtain the MeAPO-31 molecular sieve after centrifuging then, washing, drying, the roasting; Metal-salt described in the step 1 is magnesium salts, cobalt salt, manganese salt, molysite, chromic salts, titanium salt, mantoquita, zinc salt or vanadic salts.
2. the synthetic heteroatoms of a kind of microwave heating according to claim 1 replaces the method for MeAPO-31 molecular sieve, it is characterized in that the described magnesium salts of step 1 is magnesium acetate or magnesium nitrate, described cobalt salt is rose vitriol, Xiao Suangu or Cobaltous diacetate, described manganese salt is manganese acetate or manganous sulfate, described molysite is iron nitrate or ferric sulfate, described chromic salts is chromium nitrate or chromium acetate, described titanium salt is titanium chloride or tetrabutyl titanate, described mantoquita is cupric nitrate, copper sulfate or cupric chloride, described zinc salt is zinc acetate, zinc nitrate or zinc sulfate, and described vanadic salts is an ammonium vanadate.
3. the synthetic heteroatoms of a kind of microwave heating according to claim 2 replaces the method for MeAPO-31 molecular sieve, and the mass ratio that it is characterized in that described strong phosphoric acid of step 1 and water is 1: 2.7～3.8.
4. the synthetic heteroatoms of a kind of microwave heating according to claim 3 replaces the method for MeAPO-31 molecular sieve, and the mass ratio that it is characterized in that described strong phosphoric acid of step 1 and Di-n-Butyl Amine is 1: 0.7～0.9.
5. the synthetic heteroatoms of a kind of microwave heating according to claim 4 replaces the method for MeAPO-31 molecular sieve, and the mass ratio that it is characterized in that described strong phosphoric acid of step 1 and metal-salt is 0.06～0.8.
6. the synthetic heteroatoms of a kind of microwave heating according to claim 5 replaces the method for MeAPO-31 molecular sieve, and the mass ratio that it is characterized in that described strong phosphoric acid of step 1 and aluminum isopropylate is 1.6～1.9.
7. the synthetic heteroatoms of a kind of microwave heating according to claim 5 replaces the method for MeAPO-31 molecular sieve, and the mass ratio that it is characterized in that described strong phosphoric acid of step 1 and pseudo-boehmite is 0.4～1.0.
8. according to the method for claim 6 or the synthetic heteroatoms replacement of 7 described a kind of microwave heatings MeAPO-31 molecular sieve, it is characterized in that the described crystallization temperature of step 2 is 140～180 ℃, crystallization time is 1h～2.5h.
9. the synthetic heteroatoms of a kind of microwave heating according to claim 8 replaces the method for MeAPO-31 molecular sieve, it is characterized in that drying temperature described in the step 2 is 100 ℃～120 ℃, and be 12h～24h time of drying.
10. the synthetic heteroatoms of a kind of microwave heating according to claim 9 replaces the method for MeAPO-31 molecular sieve, it is characterized in that maturing temperature described in the step 2 is 500～600 ℃, and roasting time is 2h～6h.
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| CN102513148B (en) * | 2011-12-12 | 2013-10-09 | 南京工业大学 | Catalyst and process for coproduction of benzaldehyde and acyl chloride by benzal chloride acidolysis reaction |
| CN105776238A (en) * | 2014-12-17 | 2016-07-20 | 中国科学院大连化学物理研究所 | Ionothermal synthesis method of LAU type metal aluminum phosphate molecular sieve |
| CN104525105A (en) * | 2015-01-12 | 2015-04-22 | 国家电网公司 | Preparation method for microwave phosphorus ammonium type zeolite material for desulfurization waste water |
| CN105600800A (en) * | 2016-03-18 | 2016-05-25 | 黑龙江大学 | Method for synthesizing CoAPO-41 molecular sieve |
| CN113277530A (en) * | 2021-06-08 | 2021-08-20 | 深圳技术大学 | Niobium-doped AlPO-31 molecular sieve crystal and preparation method thereof |
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