CN105129815A - Preparation method of crystalline-state silico-aluminum-phosphate material - Google Patents
Preparation method of crystalline-state silico-aluminum-phosphate material Download PDFInfo
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Abstract
The invention relates to a preparation method of a crystalline-state silico-aluminum-phosphate material. The preparation method includes following steps: 1) ball-milling zeolite molecular sieve raw powder for 0.5-24 h, adding the ball-milled zeolite molecular sieve raw powder to an inorganic acid solution, and activating the zeolite molecular sieve raw powder at 60-120 DEG C to prepare a crystal seed solution; 2) filling a high-pressure reaction kettle with a phosphorus source, an aluminum source, a silicon source, an organic template agent R and deionized water to prepare a molecular sieve crystallization pre-colloid solution, adding the crystal seed solution, fully stirring and uniformly mixing the solutions, performing crystallization at 130-220 DEG C under a self-generated pressure for 1-24 h; and 3) performing pressure relief at a certain degree to the synthetic reaction kettle system under an in-site high-temperature condition, closing and sealing the high-pressure reaction kettle, and performing further crystallization at the crystallization temperature of 130-220 DEG C for the crystallization time of 2-60 h to prepare the crystalline-state silico-aluminum-phosphate material.
Description
Technical field
The present invention relates to a kind of preparation method of crystal form silicon aluminium phosphate material, specifically, the invention relates to and carry out pressure discharge operations, the method for one step hydro thermal method synthesized silicon-aluminum phosphate molecular sieve material by under hot conditions in position.
Background technology
1984, American Association Carbide (UCC) developed a series of silicoaluminophosphamolecular molecular sieves (SAPO-n), is by SiO
2, AlO
2 -, PO
2 +the microporous inorganic material that three kinds of tetrahedron elements are formed, be with organic amine be template, respectively with hydrated aluminum oxide, phosphoric acid, silicon sol be aluminium source, phosphorus source and silicon source, by what obtain after hydrothermal crystallization method, roasting removing template.The basic building-up process of silicoaluminophosphamolecular molecular sieves (SAPO-n) is: silicon source, aluminium source, phosphorus source, template and water are measured according to a certain percentage, under the condition stirred, raw material is mixed in a certain order, fully stir into gel, crystallization certain hour at certain temperature and autogenous pressure, can obtain silicoaluminophosphamolecular molecular sieves by after solid product separation, washing, drying after crystallization is complete.Existingly to prepare in the method for silicoaluminophosphamolecular molecular sieves material conventional template and comprise one or more the mixture such as diethylamine, triethylamine, Isopropylamine, tetraethyl ammonium hydroxide, morpholine, piperidines.
Because the skeleton structure of silicon aluminium phosphate SAPO molecular sieve is by SiO
2, AlO
2 -, PO
2 +three kinds of tetrahedrons are interconnected by certain way and form.For SAPO molecular sieve, template has considerable influence to the composition of the generation of nucleus, the growth of crystal grain and synthetic product, acidity, thus has a huge impact the structure of silicoaluminophosphamolecular molecular sieves, stability and catalytic performance.The acid-basicity of different templates agent self is different, water-soluble also different, the kind of template and consumption all can have an impact to the existence of Si, P, Al in final product, thus cause the change of product structure type, the final acidic nature affecting SAPO molecular sieve surface, as tetraethyl ammonium hydroxide is conducive to the skeleton that Si element enters SAPO molecular sieve equably, and triethylamine is conducive to the formation of strong acid center in framework of molecular sieve.
At present, report that the synthetic method of maximum silicoaluminophosphamolecular molecular sieves is hydrothermal synthesis method, research contents mainly concentrates on the control of SAPO framework of molecular sieve silicone content and the adjustment of grain-size.The method of a kind of two step synthesis low silicon SAPO-34 molecular sieve is disclosed for SAPO-34: CN10233413A, namely the Primogel of synthesizing high-silicon SAPO-34 is first prepared, crystallization certain hour at suitable temperature, then the gel that aluminum phosphate and organic amine are formed is added in above-mentioned high silicon SAPO-34 system, continue crystallization and the low silicon SAPO-34 molecular sieve of final acquisition.CN102285669B discloses one and prepares the method that skeleton is rich in the SAPO-34 molecular sieve of Si (4Al) structure, first mixed by the composite mould plate agent that aluminium source, fluorochemical are formed with organic amine template, add phosphorus source more successively, the order of addition(of ingredients) in silicon source prepares Primogel, increase Al atomic space steric hindrance, improve Si to the replacement probability of P, the SAPO-34 molecular sieve of Si (4Al) coordination structure is rich in preparation, the strength of acid of regulation and control SAPO-34 molecular sieve, sour density, the controlled synthesis realizing molecular sieve and stably manufactured.CN101823728A discloses a kind of preparation method of fine grain SAPO-34 molecular sieve, by Hydrothermal Synthesis gel and burin-in process, is utilizing hydrogen peroxide oxidation process, eventually passes ultrasonic disperse and vacuum-drying obtains fine grain SAPO-34 molecular sieve.
In fact, in silicon aluminium phosphate SAPO Crystallization of Zeolite building-up process, the pH of synthesis mother liquid can occur to change significantly before and after crystallization, the pH of the mother liquor namely after crystallization can obviously increase, not only can affect degree of crystallinity and the yield of zeolite product, also can affect the distribution of Si in framework of molecular sieve and co-ordination state.Be organic amine in conjunction with the template used in silicon aluminium phosphate SAPO sieve synthesis procedure, there is certain volatility, therefore, by pressure discharge operations release portion organic amine template under hot conditions in position, thus accomplish that the pH regulating and controlling synthesis mother liquid in crystallization process is to the synthesis of control SAPO molecular sieve, about the technology of this respect, there is not been reported.
Summary of the invention
The invention provides a kind of novel processing step of crystal form silicon aluminium phosphate material, technical barrier to be solved mainly hydrothermal method prepare that the relative crystallinity of silicoaluminophosphamolecular molecular sieves material is low, yield is low, silicone content and the unmanageable problem that distributes, and active low and the life-span is short and the problem of hydrothermal stability difference in SCR (SCR) process when this silicoaluminophosphamolecular molecular sieves material is used for methanol-to-olefins reaction.Crystal form silicon aluminium phosphate material obtained by the inventive method has that relative crystallinity is high, catalytic activity is high, and the life-span is long, the feature of good hydrothermal stability, and during the silicon aluminium phosphate material prepared by the method, the yield of product is higher.
In order to solve above-mentioned technical barrier and meet the application requiring of crystal form silicon aluminium phosphate material in different field, the technical solution used in the present invention is as described below: a kind of preparation method of crystal form silicon aluminium phosphate material, and the method comprises the following steps:
(1) synthesis of seed-solution: former for zeolite molecular sieve powder is pulverized ball milling 0.5 ~ 24 hour through ball mill, and then join in inorganic acid solution by the molecular screen primary powder after ball milling, activation treatment at 60 ~ 120 DEG C of temperature, namely obtains seed-solution;
(2) phosphorus source, aluminium source, silicon source, organic formwork agent R and deionized water are added in autoclave prepare colloidal solution before Crystallization of Zeolite, then seed-solution is added, through stirring mixing, at 130 ~ 220 DEG C, first Crystallizing treatment 1 ~ 24 hour under autogenous pressure;
(3) in position under hot conditions to the pressure discharge operations that synthesis reaction kettle body system carries out to a certain degree, then close and sealed high pressure reactor, in Crystallizing treatment temperature, that to be 130 ~ 220 DEG C and Crystallizing treatment time be is 2 ~ 60 at present little, further Crystallizing treatment, obtains crystal form silicon aluminium phosphate material.
Mineral acid in step of the present invention (1) comprises phosphoric acid, hydrochloric acid, nitric acid, a kind of or several arbitrarily mixture in sulfuric acid, and the mass percent concentration of inorganic acid solution is 0.05% ~ 5%.
Mineral acid in step of the present invention (1) is preferably the phosphoric acid solution that mass percent concentration is 0.3% ~ 1.5%.
In step of the present invention (1), preferably activating treatment temperature is 70 ~ 110 DEG C, and the treatment time is 1 ~ 12 hour.
The mol ratio composition of each material added during colloidal solution before preparing Crystallization of Zeolite in step of the present invention (2) is with Al
2o
3, SiO
2, P
2o
5, H
2o, R count Al
2o
3: aSiO
2: bP
2o
5: cH
2o:dR, wherein R is organic formwork agent, and the scope of the scope of a to be the scope of 0.05 ~ 2, b be 0.5 ~ 3, c is the scope of 10 ~ 200, d is 0.5 ~ 6.
Phosphorus source in step of the present invention (2) comprises a kind of or several arbitrarily mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or phosphorous oxides.
Aluminium source in step of the present invention (2) comprises a kind of or several arbitrarily mixture in pseudo-boehmite, aluminum isopropylate, aluminium salt, hydrated aluminum oxide, aluminum alkoxide, Alumina gel, activated alumina.
Silicon source in step of the present invention (2) comprises a kind of or several arbitrarily mixture in silicon sol, active silica, positive silicon ester.
Phosphorus source in step of the present invention (2) is preferably ortho-phosphoric acid, and silicon source is preferably silicon sol, and aluminium source is preferably pseudo-boehmite.
Organic formwork agent R in step of the present invention (2) comprises a kind of or several arbitrarily mixture in triethylamine, diethylamine, di-n-propylamine, Diisopropylamine, morpholine, DIPEA, tetraethyl ammonium hydroxide.
The pressure release scope of the pressure discharge operations part in step of the present invention (3) is 0.1 ~ 40% of autogenous pressure in the reactor under crystallization temperature.
The pressure release scope of the pressure discharge operations part in step of the present invention (3) is preferably 5% ~ 30% of autogenous pressure in the reactor under crystallization temperature.
In step of the present invention (3), better pressure release scope is 5% ~ 30% of autogenous pressure in reactor, and the crystallization temperature of reactor is preferably 160 ~ 200 DEG C.
The gas that pressure discharge operations in step of the present invention (3) discharges carries out condensation recycle and reuse.
The building-up process of step of the present invention (1), step (2), step (3) is all in continuously stirring or to carry out under rotating.
It is silicoaluminophosphamolecular molecular sieves material that preparation method of the present invention obtains crystal form silicon aluminium phosphate material, comprises SAPO-5, SAPO-11, SAPO-18 and SAPO-34.
The present invention is by in-situ high temperature pressure discharge operations synthesized silicon-aluminum phosphate molecular sieve material, improve yield and the relative crystallinity of product, silicone content in silicoaluminophosphamolecular molecular sieves material and distribution can be regulated by the Reasonable Regulation And Control of pressure discharge operations, obtain acid amount large, the silicoaluminophosphamolecular molecular sieves material that strength of acid is moderate, when it can be used as catalyzer to react for methanol-to-olefins reaction, catalytic activity significantly improves, and catalytic life obviously increases; When being used for SCR selective catalytic reduction reaction as carrier, hydrothermal stability obviously strengthens, and achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is comparative example 1, embodiment 1, embodiment 2, the X-ray diffraction spectrogram (XRD) of product S APO-34 molecular sieve synthesized by embodiment 3 and embodiment 4.
Fig. 2 is comparative example 2, embodiment 5, embodiment 6, the X-ray diffraction spectrogram (XRD) of product S APO-5 molecular sieve synthesized by embodiment 7 and embodiment 8.
Fig. 3 is comparative example 3, embodiment 9, embodiment 10, the X-ray diffraction spectrogram (XRD) of product S APO-11 molecular sieve synthesized by embodiment 11 and embodiment 12.
Fig. 4 is comparative example 4, embodiment 13, embodiment 14, the X-ray diffraction spectrogram (XRD) of product S APO-18 molecular sieve synthesized by embodiment 15 and embodiment 16.
Embodiment
Below in conjunction with accompanying drawing 1 ~ 4, by embodiment, the present invention is further elaborated, but protection scope of the present invention is in no way limited to these embodiments.
Comparative example 1
By SAPO-34 molecular screen primary powder after 3 hours ball-milling processing, join in the phosphoric acid solution of 0.5%, at 90 DEG C, activation treatment obtains the SAPO-34 molecular sieve crystal seed liquid that massfraction is 50% after 6 hours; Then respectively with pseudo-boehmite, ortho-phosphoric acid, silicon sol for raw material, with triethylamine (TEA) for template, according to feed molar proportioning composition with Al
2o
3, SiO
2, P
2o
5, H
2o, R count Al
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:3TEA feeds in raw material, and in 200L autoclave, prepare colloidal solution before SAPO-34 Crystallization of Zeolite, then add the SAPO-34 molecular sieve crystal seed liquid that above-mentioned massfraction is 50%, at 200 DEG C, Crystallizing treatment 40 hours, obtains SAPO-34 zeolite product; After autoclave cooling, through being separated, washing, roasting 5 hours at 550 DEG C after drying.Product yield is 61%, and specifies that the degree of crystallinity of this SAPO-34 molecular sieve is 100%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 1.
Comparative example 2
By SAPO-5 molecular screen primary powder after 3 hours ball-milling processing, join in the phosphoric acid solution of 0.5%, at 90 DEG C, activation treatment obtains the SAPO-5 molecular sieve crystal seed liquid that massfraction is 50% after 6 hours; Then respectively with pseudo-boehmite, ortho-phosphoric acid, silicon sol for raw material, with triethylamine (TEA) for template, according to feed molar proportioning composition with Al
2o
3, SiO
2, P
2o
5, H
2o, R count Al
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:1TEA feeds in raw material, and in 200L autoclave, prepare colloidal solution before SAPO-5 Crystallization of Zeolite, then add the SAPO-5 molecular sieve crystal seed liquid that above-mentioned massfraction is 50%, at 200 DEG C, Crystallizing treatment 40 hours, obtains SAPO-5 zeolite product; After autoclave cooling, through being separated, washing, roasting 5 hours at 550 DEG C after drying.Product yield is 55%, and specifies that the degree of crystallinity of this SAPO-5 molecular sieve is 100%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 2.
Comparative example 3
By SAPO-11 molecular screen primary powder after 3 hours ball-milling processing, join in the phosphoric acid solution of 0.5%, at 90 DEG C, activation treatment obtains the SAPO-11 molecular sieve crystal seed liquid that massfraction is 50% after 6 hours; Then respectively with pseudo-boehmite, ortho-phosphoric acid, silicon sol for raw material, with di-n-propylamine (DPA) for template, according to feed molar proportioning composition with Al
2o
3, SiO
2, P
2o
5, H
2o, R count Al
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:1.2DPA feeds in raw material, and in 200L autoclave, prepare colloidal solution before SAPO-11 Crystallization of Zeolite, then add the SAPO-11 molecular sieve crystal seed liquid that above-mentioned massfraction is 50%, at 200 DEG C, Crystallizing treatment 40 hours, obtains SAPO-11 zeolite product; After autoclave cooling, through being separated, washing, roasting 5 hours at 550 DEG C after drying.Product yield is 58%, and specifies that the degree of crystallinity of this SAPO-11 molecular sieve is 100%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 3.
Comparative example 4
By SAPO-18 molecular screen primary powder after 3 hours ball-milling processing, join in the phosphoric acid solution of 0.5%, at 90 DEG C, activation treatment obtains the SAPO-18 molecular sieve crystal seed liquid that massfraction is 50% after 6 hours; Then respectively with pseudo-boehmite, ortho-phosphoric acid, silicon sol for raw material, with DIPEA (DIPEA) for template, according to feed molar proportioning composition with Al
2o
3, SiO
2, P
2o
5, H
2o, R count Al
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:3DIPEA feeds in raw material, and in 200L autoclave, prepare colloidal solution before SAPO-18 Crystallization of Zeolite, then add the SAPO-18 molecular sieve crystal seed liquid that above-mentioned massfraction is 50%, at 200 DEG C, Crystallizing treatment 40 hours, obtains SAPO-18 zeolite product; After autoclave cooling, through being separated, washing, roasting 5 hours at 550 DEG C after drying.Product yield is 57%, and specifies that the degree of crystallinity of this SAPO-18 molecular sieve is 100%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 4.
Embodiment 1
By SAPO-34 molecular screen primary powder after 3 hours ball-milling processing, join in the phosphoric acid solution of 0.5%, at 90 DEG C, activation treatment obtains the SAPO-34 molecular sieve crystal seed liquid that massfraction is 50% after 6 hours; Respectively with pseudo-boehmite, ortho-phosphoric acid, silicon sol for raw material, with triethylamine (TEA) for template, according to feed molar proportioning composition with Al
2o
3, SiO
2, P
2o
5, H
2o, R count Al
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:3TEA feeds in raw material, colloidal solution before SAPO-34 Crystallization of Zeolite is prepared in 200L autoclave, then the SAPO-34 molecular sieve crystal seed mother liquor that above-mentioned massfraction is 50% is added, first Crystallizing treatment 10 hours at 200 DEG C, carry out pressure discharge operations at this moment, pressure release scope is 5%, then closes and sealing autoclave, Crystallizing treatment 30 hours at 200 DEG C, obtains SAPO-34 zeolite product further; After autoclave cooling, through being separated, washing, roasting 5 hours at 550 DEG C after drying.The SAPO-34 zeolite product yield finally obtained is 88%, and degree of crystallinity is 133%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 1.
Embodiment 2
According to each Step By Condition of embodiment 1, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:3.5TEA, changes the pressure release scope in pressure discharge operations process into 10%, and the SAPO-34 zeolite product yield finally obtained is 91%, and degree of crystallinity is 138%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 1.
Embodiment 3
According to each Step By Condition of embodiment 1, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:3.8TEA, changes the pressure release scope in pressure discharge operations process into 20%, and the SAPO-34 zeolite product yield finally obtained is 93%, and degree of crystallinity is 143%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 1.
Embodiment 4
According to each Step By Condition of embodiment 1, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R count, and change Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:4.3TEA, changes the pressure release scope in pressure discharge operations process into 30%, and the SAPO-34 zeolite product yield finally obtained is 94%, and degree of crystallinity is 142%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 1.
Embodiment 5
By SAPO-5 molecular screen primary powder after 3 hours ball-milling processing, join in the phosphoric acid solution of 0.5%, at 90 DEG C, activation treatment obtains the SAPO-5 molecular sieve crystal seed liquid that massfraction is 50% after 6 hours; Respectively with pseudo-boehmite, ortho-phosphoric acid, silicon sol for raw material, with triethylamine (TEA) for template, according to feed molar proportioning composition with Al
2o
3, SiO
2, P
2o
5, H
2o, R count Al
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:1.2TEA feeds in raw material, colloidal solution before SAPO-34 Crystallization of Zeolite is prepared in 200L autoclave, then the SAPO-5 molecular sieve crystal seed mother liquor that above-mentioned massfraction is 50% is added, first Crystallizing treatment 10 hours at 200 DEG C, carry out pressure discharge operations at this moment, pressure release scope is 5%, then closes and sealing autoclave, Crystallizing treatment 30 hours at 200 DEG C, obtains SAPO-5 zeolite product further; After autoclave cooling, through being separated, washing, roasting 5 hours at 550 DEG C after drying.The SAPO-5 zeolite product yield finally obtained is 84%, and degree of crystallinity is 135%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 2.
Embodiment 6
According to each Step By Condition of embodiment 5, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:1.5TEA, and change the pressure release scope in pressure discharge operations process into 10%, the SAPO-5 zeolite product yield finally obtained is 89%, and degree of crystallinity is 141%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 2.
Embodiment 7
According to each Step By Condition of embodiment 5, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:1.8TEA, and change the pressure release scope in pressure discharge operations process into 20%, the SAPO-5 zeolite product yield finally obtained is 92%, and degree of crystallinity is 145%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 2.
Embodiment 8
According to each Step By Condition of embodiment 5, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:2.1TEA, and change the pressure release scope in pressure discharge operations process into 30%, the SAPO-5 zeolite product yield finally obtained is 95%, and degree of crystallinity is 144%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 2.
Embodiment 9
By SAPO-11 molecular screen primary powder after 3 hours ball-milling processing, join in the phosphoric acid solution of 0.5%, at 90 DEG C, activation treatment obtains the SAPO-11 molecular sieve crystal seed liquid that massfraction is 50% after 6 hours; Respectively with pseudo-boehmite, ortho-phosphoric acid, silicon sol for raw material, with di-n-propylamine (DPA) for template, according to feed molar proportioning composition with Al
2o
3, SiO
2, P
2o
5, H
2o, R count Al
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:1.4DPA feeds in raw material, colloidal solution before SAPO-11 Crystallization of Zeolite is prepared in 200L autoclave, then the SAPO-11 molecular sieve crystal seed mother liquor that above-mentioned massfraction is 50% is added, first Crystallizing treatment 10 hours at 200 DEG C, carry out pressure discharge operations at this moment, pressure release scope is 5%, then closes and sealing autoclave, Crystallizing treatment 30 hours at 200 DEG C, obtains SAPO-11 zeolite product further; After autoclave cooling, through being separated, washing, roasting 5 hours at 550 DEG C after drying.The SAPO-11 zeolite product yield finally obtained is 85%, and degree of crystallinity is 137%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 3.
Embodiment 10
According to each Step By Condition of embodiment 9, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:1.8DPA, and change the pressure release scope in pressure discharge operations process into 10%, the SAPO-11 zeolite product yield finally obtained is 90%, and degree of crystallinity is 150%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 3.
Embodiment 11
According to each Step By Condition of embodiment 9, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:2.2DPA, and change the pressure release scope in pressure discharge operations process into 20%, the SAPO-11 zeolite product yield finally obtained is 91%, and degree of crystallinity is 151%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 3.
Embodiment 12
According to each Step By Condition of embodiment 9, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:2.6DPA, and change the pressure release scope in pressure discharge operations process into 30%, the SAPO-11 zeolite product yield finally obtained is 93%, and degree of crystallinity is 153%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 3.
Embodiment 13
By SAPO-18 molecular screen primary powder after 3 hours ball-milling processing, join in the phosphoric acid solution of 0.5%, at 90 DEG C, activation treatment obtains the SAPO-18 molecular sieve crystal seed liquid that massfraction is 50% after 6 hours; Respectively with pseudo-boehmite, ortho-phosphoric acid, silicon sol for raw material, with DIPEA (DIPEA) for template, according to feed molar proportioning composition with Al
2o
3, SiO
2, P
2o
5,h
2o, R count Al
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:2DEA:3.2DIPEA feeds in raw material, colloidal solution before SAPO-18 Crystallization of Zeolite is prepared in 200L autoclave, then the SAPO-18 molecular sieve crystal seed mother liquor that above-mentioned massfraction is 50% is added, first Crystallizing treatment 10 hours at 200 DEG C, carry out pressure discharge operations at this moment, pressure release scope is 5%, then closes and sealing autoclave, Crystallizing treatment 30 hours at 200 DEG C, obtains SAPO-18 zeolite product further; After autoclave cooling, through being separated, washing, roasting 5 hours at 550 DEG C after drying.The SAPO-18 zeolite product yield finally obtained is 86%, and degree of crystallinity is 148%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 4.
Embodiment 14
According to each Step By Condition of embodiment 13, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:3.5DIPEA.And changing the pressure release scope in pressure discharge operations process into 10%, the SAPO-18 zeolite product yield finally obtained is 91%, and degree of crystallinity is 151%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 4.
Embodiment 15
According to each Step By Condition of embodiment 13, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:3.8DIPEA, and change the pressure release scope in pressure discharge operations process into 20%, the SAPO-18 zeolite product yield finally obtained is 92%, and degree of crystallinity is 154%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 4.
Embodiment 16
According to each Step By Condition of embodiment 13, but during batching, feed molar proportioning is with Al
2o
3, SiO
2, P
2o
5, H
2o, R meter changes Al into
2o
3: 0.4SiO
2: P
2o
5: 50H
2o:4.1DIPEA, and change the pressure release scope in pressure discharge operations process into 30%, the SAPO-18 zeolite product yield finally obtained is 92%, and degree of crystallinity is 153%.The X-ray diffraction spectrogram (XRD) of gained sample is shown in Fig. 4.
The actual pressure discharge operations condition of all comparative examples and embodiment, the yield of products obtained therefrom and relative crystallinity and hydrothermal stability test result all list in table 1.
Table 1
Claims (15)
1. a preparation method for crystal form silicon aluminium phosphate material, is characterized in that the method comprises the following steps:
(1) synthesis of seed-solution: former for zeolite molecular sieve powder is pulverized ball milling 0.5 ~ 24 hour through ball mill, and then join in inorganic acid solution by the molecular screen primary powder after ball milling, activation treatment at 60 ~ 120 DEG C of temperature, namely obtains seed-solution;
(2) phosphorus source, aluminium source, silicon source, organic formwork agent R and deionized water are added in autoclave prepare colloidal solution before Crystallization of Zeolite, then seed-solution is added, through stirring mixing, at 130 ~ 220 DEG C, first Crystallizing treatment 1 ~ 24 hour under autogenous pressure;
(3) in position under hot conditions to the pressure discharge operations that synthesis reaction kettle body system carries out to a certain degree, then close and sealed high pressure reactor, in Crystallizing treatment temperature, that to be 130 ~ 220 DEG C and Crystallizing treatment time be is 2 ~ 60 at present little, further Crystallizing treatment, obtains crystal form silicon aluminium phosphate material.
2. method according to claim 1, is characterized in that, the mineral acid in step (1) comprises phosphoric acid, hydrochloric acid, nitric acid, a kind of or several arbitrarily mixture in sulfuric acid, and the mass percent concentration of inorganic acid solution is 0.05% ~ 5%.
3. method according to claim 1, is characterized in that, the mineral acid in step (1) to be mass percent concentration be 0.3% ~ 1.5% phosphoric acid solution.
4. method according to claim 1, is characterized in that, the activating treatment temperature in step (1) is 70 ~ 110 DEG C, and the treatment time is 1 ~ 12 hour.
5. method according to claim 1, is characterized in that, the mol ratio composition of each material added during colloidal solution before preparing Crystallization of Zeolite in step (2) is with Al
2o
3, SiO
2, P
2o
5, H
2o, R count Al
2o
3: aSiO
2: bP
2o
5: cH
2o:dR, wherein R is organic formwork agent, and the scope of the scope of a to be the scope of 0.05 ~ 2, b be 0.5 ~ 3, c is the scope of 10 ~ 200, d is 0.5 ~ 6.
6. method according to claim 1, is characterized in that, the phosphorus source in step (2) comprises a kind of or several arbitrarily mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or phosphorous oxides.
7. method according to claim 1, it is characterized in that, the aluminium source in step (2) comprises a kind of or several arbitrarily mixture in pseudo-boehmite, aluminum isopropylate, aluminium salt, hydrated aluminum oxide, aluminum alkoxide, Alumina gel, activated alumina.
8. method according to claim 1, is characterized in that, the silicon source in step (2) comprises a kind of or several arbitrarily mixture in silicon sol, active silica, positive silicon ester.
9. method according to claim 1, is characterized in that, the phosphorus source in step (2) is ortho-phosphoric acid, and silicon source is silicon sol, and aluminium source is pseudo-boehmite.
10. method according to claim 1, it is characterized in that, organic formwork agent R in step (2) comprises a kind of or several arbitrarily mixture in triethylamine, diethylamine, di-n-propylamine, Diisopropylamine, morpholine, DIPEA, tetraethyl ammonium hydroxide.
11. methods according to claim 1, is characterized in that, the pressure release scope of the pressure discharge operations part in step (3) is 0.1 ~ 40% of autogenous pressure in the reactor under crystallization temperature.
12. methods according to claim 1, is characterized in that, the pressure release scope of the pressure discharge operations part in step (3) is 5% ~ 30% of autogenous pressure in the reactor under crystallization temperature.
13. methods according to claim 1, is characterized in that, the gas that the pressure discharge operations in step (3) discharges carries out condensation recycle and reuse.
14. methods according to claim 1, is characterized in that, the building-up process of step (1), step (2), step (3) is all in continuously stirring or to carry out under rotating.
15. methods according to claim 1, is characterized in that, described to obtain crystal form silicon aluminium phosphate material be silicoaluminophosphamolecular molecular sieves material, comprises SAPO-5, SAPO-11, SAPO-18 and SAPO-34.
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| CN112239217A (en) * | 2019-07-17 | 2021-01-19 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
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