CN105129815B - A kind of preparation method of crystalline state SAPO material - Google Patents
A kind of preparation method of crystalline state SAPO material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of crystalline state SAPO material, the method comprises the following steps：(1) former for zeolite molecular sieve powder is pulverized ball milling 0.5～24 hour through ball mill, then the molecular screen primary powder after ball milling is added in inorganic acid solution, activation processing at a temperature of 60～120 DEG C, that is, obtains seed-solution；(2) phosphorus source, silicon source, silicon source, organic formwork agent R and deionized water are added in autoclave and prepare colloid solution before Crystallization of Zeolite, it is subsequently adding seed-solution, through stirring mixing, first Crystallizing treatment 1～24 hour under 130～220 DEG C, self-generated pressure；(3) under hot conditionss, a certain degree of pressure discharge operations are carried out to synthesis reaction kettle body system in the original location, it is then shut off and seal autoclave, Crystallizing treatment temperature be 130～220 DEG C and Crystallizing treatment time be 2～60 little at present, Crystallizing treatment, obtains crystalline state SAPO material further.
Description
Technical field
The present invention relates to a kind of preparation method of crystalline state SAPO material, specifically, the present invention is with regard to passing through
Carry out pressure discharge operations, the method for one step hydro thermal method synthesized silicon-aluminum phosphate molecular sieve material in the original location under hot conditionss.
Background technology
1984, American Association Carbide (UCC) developed a series of silicoaluminophosphamolecular molecular sieves (SAPO-n), be by
SiO2、AlO2 -、PO2 +The microporous inorganic material that three kinds of tetrahedron elements are constituted, is with organic amine as template, respectively with aqua oxidation
Aluminum, phosphoric acid, Ludox are silicon source, phosphorus source and silicon source, obtain after hydrothermal crystallization method, roasting remove template.Silicon phosphate
The basic building-up process of aluminum molecular screen (SAPO-n) is：Silicon source, silicon source, phosphorus source, template and water are measured according to a certain percentage,
Under conditions of stirring, raw material is mixed in a certain order, be sufficiently stirred for into gel, in certain temperature and self-generated pressure
Lower crystallization certain time, after crystallization is complete, silicoaluminophosphamolecular molecular sieves can be obtained by after solid product separation, washing, drying.Existing
Prepare conventional template in the method for silicoaluminophosphamolecular molecular sieves material and include diethylamine, triethylamine, 2-aminopropane., tetraethyl hydrogen-oxygen
Change the mixture of one or more such as ammonium, morpholine, piperidines.
Because the framing structure of SAPO SAPO molecular sieve is by SiO2、AlO2 -、PO2 +Three kinds of tetrahedrons press certain way phase
Connect and form.For SAPO molecular sieve, template is to the composition of the generation of nucleus, the growth of crystal grain and synthetic product, acidity
There is considerable influence, thus having a huge impact to the structure of silicoaluminophosphamolecular molecular sieves, stability and catalytic performance.Different templates
The Acidity of Aikalinity of agent itself is different, and water solublity is also different, and the species of template and consumption all can be to Si, P, the Al's in final product
Existence produces impact, thus causing the change of product structure type, the final acidic nature affecting SAPO molecular sieve surface,
As tetraethyl ammonium hydroxide is conducive to Si element evenly into the skeleton of SAPO molecular sieve, and triethylamine is conducive to molecule sieve skeleton
The formation of strong acid center in frame.
At present, the synthetic method of the most silicoaluminophosphamolecular molecular sieves of report is hydrothermal synthesis method, and research contents is mainly concentrated
In the control of SAPO molecular sieve skeleton silicone content and the regulation of crystallite dimension.Taking SAPO-34 as a example：CN10233413A discloses
A kind of method of two-step method synthesizing low silicon SAPO-34 molecular sieve, prepares the Primogel of synthesizing high-silicon SAPO-34 first,
Crystallization certain time at a temperature of suitable, the gel then forming aluminum phosphate and organic amine is added to above-mentioned high silicon SAPO-34
In system, continue crystallization and finally obtain low silicon SAPO-34 molecular sieve.CN102285669B discloses one kind to be prepared skeleton and is rich in
The method of the SAPO-34 molecular sieve of Si (4Al) structure, by the compound die forming silicon source, fluoride and organic amine template
Plate agent elder generation mix homogeneously, sequentially adds phosphorus source, the charging sequence of silicon source prepares Primogel, increases Al atomic space steric hindrance,
Improve the replacement probability to P for the Si, the SAPO-34 molecular sieve rich in Si (4Al) coordination structure for the preparation, regulate and control SAPO-34 molecular sieve
Acid strength, sour density, the controllable standby realizing molecular sieve and steady production.CN101823728A discloses a kind of little crystal grain
The preparation method of SAPO-34 molecular sieve, by Hydrothermal Synthesiss gel and burin-in process, is being processed using hydrogen peroxide oxidation, finally
Obtain fine grain SAPO-34 molecular sieve through ultrasonic disperse and vacuum drying.
In fact, in SAPO SAPO molecular sieve crystallization building-up process, the pH of synthesis mother liquid can send out before and after crystallization
Life significantly changes, and that is, the pH of the mother solution after crystallization can substantially increase, and not only can affect degree of crystallinity and the yield of zeolite product,
Also distribution in framework of molecular sieve for the Si and co-ordination state can be affected.Use in conjunction with SAPO SAPO molecular sieve building-up process
Template be organic amine, there is certain volatility, therefore, had by pressure discharge operations release part under hot conditionss in the original location
Machine amine template, thus accomplish that the pH regulating and controlling synthesis mother liquid in crystallization process to control the synthesis of SAPO molecular sieve, with regard to this
There is not been reported for the technology of aspect.
Content of the invention
The present invention provides a kind of novel processing step of crystalline state SAPO material, and technical barrier to be solved is main
Be hydro-thermal method prepare silicoaluminophosphamolecular molecular sieves material relative crystallinity low, yield is low, silicone content and distribution unmanageable are asked
Topic, and this silicoaluminophosphamolecular molecular sieves material is for low and short life active during methanol-to-olefins reaction and selective catalysis
The problem of hydrothermal stability difference during reduction (SCR).Crystalline state SAPO material obtained by the inventive method has phase
, catalysis activity high to degree of crystallinity is high, life-span length, and the feature of good hydrothermal stability, during the SAPO material prepared by the method
The yield of product is higher.
In order to solve above-mentioned technical barrier and meet the application requirement in different field for the crystalline state SAPO material, this
The technical scheme of bright employing is as described below：A kind of preparation method of crystalline state SAPO material, 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, then will
Molecular screen primary powder after ball milling is added in inorganic acid solution, activation processing at a temperature of 60～120 DEG C, that is, obtain crystal seed molten
Liquid；
(2) phosphorus source, silicon source, silicon source, organic formwork agent R and deionized water are added and in autoclave, prepare molecular sieve crystalline substance
Colloid solution before change, is subsequently adding seed-solution, through stirring mixing, first brilliant under 130～220 DEG C, self-generated pressure
Change process 1～24 hour；
(3) under hot conditionss, a certain degree of pressure discharge operations are carried out to synthesis reaction kettle body system in the original location, be then shut off simultaneously
Sealing autoclave, Crystallizing treatment temperature be 130～220 DEG C and Crystallizing treatment time be 2～60 little at present, brilliant further
Change is processed, and obtains crystalline state SAPO material.
Mineral acid in step (1) of the present invention includes phosphoric acid, hydrochloric acid, nitric acid, one of sulphuric acid or arbitrarily several mixing
Compound, the mass percent concentration of inorganic acid solution is 0.05%～5%.
Mineral acid in step (1) of the present invention is preferably the phosphoric acid solution that mass percent concentration is 0.3%～1.5%.
In step (1) of the present invention, preferably activating treatment temperature is 70～110 DEG C, and process time is 1～12 hour.
The each material adding during colloid solution before preparing Crystallization of Zeolite in step (2) of the present invention mol ratio composition with
Al2O3、SiO2、P2O5、H2O, R are calculated as Al2O3:aSiO2:bP2O5:cH2O:DR, wherein R are organic formwork agent, and the scope of a is
The scope for 0.5～3, c for the scope of 0.05～2, b is the scope of 10～200, d is 0.5～6.
Phosphorus source in step (2) of the present invention includes orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphorus compound or phosphorus oxygen
One of compound or arbitrarily several mixture.
Silicon source in step (2) of the present invention includes boehmite, aluminum isopropylate., aluminium salt, hydrated alumina, alkoxyl
One of aluminum, Alumina gel, activated alumina or arbitrarily several mixture.
Silicon source in step (2) of the present invention includes one of Ludox, active silica, positive esters of silicon acis or arbitrarily several
The mixture planted.
Phosphorus source in step (2) of the present invention is preferably orthophosphoric acid, and silicon source is preferably Ludox, and silicon source preferably intends thin water aluminum
Stone.
Organic formwork agent R in step (2) of the present invention include triethylamine, diethylamine, di-n-propylamine, diisopropylamine, morpholine,
One of N, N- diisopropylethylamine, tetraethyl ammonium hydroxide or arbitrarily several mixture.
The pressure release scope of the pressure discharge operations part in step (3) of the present invention is self-generated pressure in the reactor under crystallization temperature
0.1～40%.
The pressure release scope of the pressure discharge operations part in step (3) of the present invention is preferably spontaneous in the reactor under crystallization temperature
The 5%～30% of pressure.
In step (3) of the present invention, preferable pressure release scope is 5%～30% of self-generated pressure in reactor, the crystallization of reactor
Preferably 160～200 DEG C of temperature.
The gas that pressure discharge operations in step (3) of the present invention are discharged carries out condensing recycle and reuse.
Step (1) of the present invention, step (2), the building-up process of step (3) are all carried out under continuous stirring or rotation.
Obtained by preparation method of the present invention, crystalline state SAPO material is silicoaluminophosphamolecular molecular sieves material, including SAPO-
5, SAPO-11, SAPO-18 and SAPO-34.
The present invention passes through in-situ high temperature pressure discharge operations synthesized silicon-aluminum phosphate molecular sieve material, improves yield and the phase of product
To degree of crystallinity, silicone content and the distribution in silicoaluminophosphamolecular molecular sieves material can be adjusted by the Reasonable Regulation And Control of pressure discharge operations, obtain
Arrive sour amount big, the moderate silicoaluminophosphamolecular molecular sieves material of acid strength, it is used for methanol as catalyst and convert low-carbon (LC) alkene processed
During hydrocarbon reaction, catalysis activity significantly improves, and catalytic life substantially increases；It is used for SCR selective catalytic reduction reaction as carrier
When, hydrothermal stability is remarkably reinforced, and achieves preferable technique effect.
Brief description
Fig. 1 is comparative example 1, embodiment 1, embodiment 2, embodiment 3 and product SAPO-34 molecular sieve synthesized by embodiment 4
X-ray diffraction spectrogram (XRD).
Fig. 2 is comparative example 2, embodiment 5, embodiment 6, embodiment 7 and product SAPO-5 molecular sieve synthesized by embodiment 8
X-ray diffraction spectrogram (XRD).
Fig. 3 is comparative example 3, embodiment 9, embodiment 10, embodiment 11 and product SAPO-11 molecule synthesized by embodiment 12
The X-ray diffraction spectrogram (XRD) of sieve.
Fig. 4 is comparative example 4, embodiment 13, embodiment 14, and embodiment 15 and product SAPO-18 synthesized by embodiment 16 divide
The X-ray diffraction spectrogram (XRD) of son sieve.
Specific embodiment
Below in conjunction with the accompanying drawings 1～4, by embodiment, the present invention is further elaborated, but protection scope of the present invention is determined
It is not limited to these embodiments.
Comparative example 1
By SAPO-34 molecular screen primary powder after 3 hours ball-milling treatment, it is added in 0.5% phosphoric acid solution, at 90 DEG C
Activation processing obtains the SAPO-34 molecular sieve seed liquid that mass fraction is 50% after 6 hours；Then respectively with boehmite,
Orthophosphoric acid, Ludox are raw material, with triethylamine (TEA) as template, form according to feed molar proportioning with Al2O3、SiO2、
P2O5、H2O, R are calculated as Al2O3:0.4SiO2:P2O5:50H2O:3TEA feeds, and in 200L autoclave, preparation SAPO-34 divides
Colloid solution before son sieve crystallization, is subsequently adding the SAPO-34 molecular sieve seed liquid that above-mentioned mass fraction is 50%, at 200 DEG C
Crystallizing treatment 40 hours, obtains SAPO-34 zeolite product；After autoclave cooling after, after separating, washing, drying
Roasting 5 hours at 550 DEG C.Product yield be 61%, and specify this SAPO-34 molecular sieve degree of crystallinity be 100%.Gained sample
X-ray diffraction spectrogram (XRD) see Fig. 1.
Comparative example 2
By SAPO-5 molecular screen primary powder after 3 hours ball-milling treatment, it is added in 0.5% phosphoric acid solution, at 90 DEG C
Activation processing obtains the SAPO-5 molecular sieve seed liquid that mass fraction is 50% after 6 hours；Then respectively with boehmite, just
Phosphoric acid, Ludox are raw material, with triethylamine (TEA) as template, form according to feed molar proportioning with Al2O3、SiO2、P2O5、
H2O, R are calculated as Al2O3:0.4SiO2:P2O5:50H2O:1TEA feeds, and in 200L autoclave, preparation SAPO-5 molecular sieve is brilliant
Colloid solution before change, is subsequently adding the SAPO-5 molecular sieve seed liquid that above-mentioned mass fraction is 50%, Crystallizing treatment at 200 DEG C
40 hours, obtain SAPO-5 zeolite product；After autoclave cooling, roast at 550 DEG C after separating, washing, drying
Burn 5 hours.Product yield be 55%, and specify this SAPO-5 molecular sieve degree of crystallinity be 100%.The X-ray of gained sample is spread out
Penetrate spectrogram (XRD) and see Fig. 2.
Comparative example 3
By SAPO-11 molecular screen primary powder after 3 hours ball-milling treatment, it is added in 0.5% phosphoric acid solution, at 90 DEG C
Activation processing obtains the SAPO-11 molecular sieve seed liquid that mass fraction is 50% after 6 hours；Then respectively with boehmite,
Orthophosphoric acid, Ludox are raw material, with di-n-propylamine (DPA) as template, form according to feed molar proportioning with Al2O3、SiO2、
P2O5、H2O, R are calculated as Al2O3:0.4SiO2:P2O5:50H2O:1.2DPA feeds, and prepares SAPO-11 in 200L autoclave
Colloid solution before Crystallization of Zeolite, is subsequently adding the SAPO-11 molecular sieve seed liquid that above-mentioned mass fraction is 50%, at 200 DEG C
Lower Crystallizing treatment 40 hours, obtains SAPO-11 zeolite product；After autoclave cooling, after separating, washing, drying
Roasting 5 hours at 550 DEG C.Product yield be 58%, and specify this SAPO-11 molecular sieve degree of crystallinity be 100%.Gained sample
The X-ray diffraction spectrogram (XRD) of product is shown in Fig. 3.
Comparative example 4
By SAPO-18 molecular screen primary powder after 3 hours ball-milling treatment, it is added in 0.5% phosphoric acid solution, at 90 DEG C
Activation processing obtains the SAPO-18 molecular sieve seed liquid that mass fraction is 50% after 6 hours；Then respectively with boehmite,
Orthophosphoric acid, Ludox be raw material, with DIPEA (DIPEA) as template, according to feed molar proportioning form with
Al2O3、SiO2、P2O5、H2O, R are calculated as Al2O3:0.4SiO2:P2O5:50H2O:3DIPEA feeds, and makes in 200L autoclave
Colloid solution before standby SAPO-18 Crystallization of Zeolite, is subsequently adding the SAPO-18 molecular sieve seed that above-mentioned mass fraction is 50%
Liquid, Crystallizing treatment 40 hours at 200 DEG C, obtain SAPO-18 zeolite product；After autoclave cooling, separated, wash
Wash, be dried after at 550 DEG C roasting 5 hours.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 treatment, it is added in 0.5% phosphoric acid solution, at 90 DEG C
Activation processing obtains the SAPO-34 molecular sieve seed liquid that mass fraction is 50% after 6 hours；Respectively with boehmite, positive phosphorus
Acid, Ludox are raw material, with triethylamine (TEA) as template, form according to feed molar proportioning with Al2O3、SiO2、P2O5、
H2O, R are calculated as Al2O3:0.4SiO2:P2O5:50H2O:3TEA feeds, and prepares SAPO-34 molecular sieve in 200L autoclave
Colloid solution before crystallization, is subsequently adding the SAPO-34 molecular sieve seed mother solution that above-mentioned mass fraction is 50%, at 200 DEG C first
Crystallizing treatment 10 hours, carries out pressure discharge operations at this moment, and pressure release scope is 5%, is then shut off and sealing autoclave, exists further
Crystallizing treatment 30 hours at 200 DEG C, obtain SAPO-34 zeolite product；After autoclave cooling, separating, washing, dry
After dry at 550 DEG C roasting 5 hours.The SAPO-34 zeolite product yield finally obtaining is 88%, and degree of crystallinity is 133%.Institute
The X-ray diffraction spectrogram (XRD) obtaining sample is shown in Fig. 1.
Embodiment 2
According to each Step By Condition of embodiment 1, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:3.5TEA, the pressure release scope during pressure discharge operations is changed to 10%,
The SAPO-34 zeolite product yield finally obtaining is 91%, and degree of crystallinity is 138%.The X-ray diffraction spectrogram of gained sample
(XRD) see Fig. 1.
Embodiment 3
According to each Step By Condition of embodiment 1, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:3.8TEA, the pressure release scope during pressure discharge operations is changed to 20%,
The SAPO-34 zeolite product yield finally obtaining is 93%, and degree of crystallinity is 143%.The X-ray diffraction spectrogram of gained sample
(XRD) see Fig. 1.
Embodiment 4
According to each Step By Condition of embodiment 1, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R count, and are changed to Al2O3:0.4SiO2:P2O5:50H2O:4.3TEA, the pressure release scope during pressure discharge operations is changed to 30%,
The SAPO-34 zeolite product yield finally obtaining is 94%, and degree of crystallinity is 142%.The X-ray diffraction spectrogram of gained sample
(XRD) see Fig. 1.
Embodiment 5
By SAPO-5 molecular screen primary powder after 3 hours ball-milling treatment, it is added in 0.5% phosphoric acid solution, at 90 DEG C
Activation processing obtains the SAPO-5 molecular sieve seed liquid that mass fraction is 50% after 6 hours；Respectively with boehmite, positive phosphorus
Acid, Ludox are raw material, with triethylamine (TEA) as template, form according to feed molar proportioning with Al2O3、SiO2、P2O5、
H2O, R are calculated as Al2O3:0.4SiO2:P2O5:50H2O:1.2TEA feeds, and prepares SAPO-34 molecule in 200L autoclave
Colloid solution before sieve crystallization, is subsequently adding the SAPO-5 molecular sieve seed mother solution that above-mentioned mass fraction is 50%, at 200 DEG C first
Crystallizing treatment 10 hours, carries out pressure discharge operations at this moment, and pressure release scope is 5%, is then shut off and sealing autoclave, exists further
Crystallizing treatment 30 hours at 200 DEG C, obtain SAPO-5 zeolite product；After autoclave cooling, separating, washing, dry
After dry at 550 DEG C roasting 5 hours.The SAPO-5 zeolite product yield finally obtaining is 84%, and degree of crystallinity is 135%.Institute
The X-ray diffraction spectrogram (XRD) obtaining sample is shown in Fig. 2.
Embodiment 6
According to each Step By Condition of embodiment 5, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:1.5TEA, and the pressure release scope during pressure discharge operations is changed to
10%, the SAPO-5 zeolite product yield finally obtaining is 89%, and degree of crystallinity is 141%.The X-ray diffraction spectrum of gained sample
Figure (XRD) is shown in Fig. 2.
Embodiment 7
According to each Step By Condition of embodiment 5, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:1.8TEA, and the pressure release scope during pressure discharge operations is changed to
20%, the SAPO-5 zeolite product yield finally obtaining is 92%, and degree of crystallinity is 145%.The X-ray diffraction spectrum of gained sample
Figure (XRD) is shown in Fig. 2.
Embodiment 8
According to each Step By Condition of embodiment 5, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:2.1TEA, and the pressure release scope during pressure discharge operations is changed to
30%, the SAPO-5 zeolite product yield finally obtaining is 95%, and degree of crystallinity is 144%.The X-ray diffraction spectrum of gained sample
Figure (XRD) is shown in Fig. 2.
Embodiment 9
By SAPO-11 molecular screen primary powder after 3 hours ball-milling treatment, it is added in 0.5% phosphoric acid solution, at 90 DEG C
Activation processing obtains the SAPO-11 molecular sieve seed liquid that mass fraction is 50% after 6 hours；Respectively with boehmite, positive phosphorus
Acid, Ludox are raw material, with di-n-propylamine (DPA) as template, form according to feed molar proportioning with Al2O3、SiO2、P2O5、
H2O, R are calculated as Al2O3:0.4SiO2:P2O5:50H2O:1.4DPA feeds, and prepares SAPO-11 molecule in 200L autoclave
Colloid solution before sieve crystallization, is subsequently adding the SAPO-11 molecular sieve seed mother solution that above-mentioned mass fraction is 50%, at 200 DEG C
First Crystallizing treatment 10 hours, carries out pressure discharge operations at this moment, and pressure release scope is 5%, is then shut off and sealing autoclave, further
Crystallizing treatment 30 hours at 200 DEG C, obtain SAPO-11 zeolite product；After autoclave cooling, separating, washing,
After drying at 550 DEG C roasting 5 hours.The SAPO-11 zeolite product yield finally obtaining 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 dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:1.8DPA, and the pressure release scope during pressure discharge operations is changed to
10%, the SAPO-11 zeolite product yield finally obtaining is 90%, and degree of crystallinity is 150%.The X-ray diffraction of gained sample
Spectrogram (XRD) is shown in Fig. 3.
Embodiment 11
According to each Step By Condition of embodiment 9, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:2.2DPA, and the pressure release scope during pressure discharge operations is changed to
20%, the SAPO-11 zeolite product yield finally obtaining is 91%, and degree of crystallinity is 151%.The X-ray diffraction of gained sample
Spectrogram (XRD) is shown in Fig. 3.
Embodiment 12
According to each Step By Condition of embodiment 9, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:2.6DPA, and the pressure release scope during pressure discharge operations is changed to
30%, the SAPO-11 zeolite product yield finally obtaining is 93%, and degree of crystallinity is 153%.The X-ray diffraction of gained sample
Spectrogram (XRD) is shown in Fig. 3.
Embodiment 13
By SAPO-18 molecular screen primary powder after 3 hours ball-milling treatment, it is added in 0.5% phosphoric acid solution, at 90 DEG C
Activation processing obtains the SAPO-18 molecular sieve seed liquid that mass fraction is 50% after 6 hours；Respectively with boehmite, positive phosphorus
Acid, Ludox are raw material, with DIPEA (DIPEA) as template, form according to feed molar proportioning with Al2O3、
SiO2、P2O5、H2O, R are calculated as Al2O3:0.4SiO2:P2O5:50H2O:2DEA:3.2DIPEA feeds, in 200L autoclave
Colloid solution before preparation SAPO-18 Crystallization of Zeolite, is subsequently adding the SAPO-18 molecular sieve seed that above-mentioned mass fraction is 50%
Mother solution, at 200 DEG C, first Crystallizing treatment 10 hours, carry out pressure discharge operations at this moment, and pressure release scope is 5%, is then shut off and close
Envelope autoclave, Crystallizing treatment 30 hours at 200 DEG C, obtain SAPO-18 zeolite product further；Treat that autoclave is lowered the temperature
Afterwards, after separating, washing, drying at 550 DEG C roasting 5 hours.The SAPO-18 zeolite product yield finally obtaining is
86%, 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 dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:3.5DIPEA.And the pressure release scope during pressure discharge operations is changed to
10%, the SAPO-18 zeolite product yield finally obtaining is 91%, and degree of crystallinity is 151%.The X-ray diffraction of gained sample
Spectrogram (XRD) is shown in Fig. 4.
Embodiment 15
According to each Step By Condition of embodiment 13, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:3.8DIPEA, and the pressure release scope during pressure discharge operations is changed to
20%, the SAPO-18 zeolite product yield finally obtaining is 92%, and degree of crystallinity is 154%.The X-ray diffraction of gained sample
Spectrogram (XRD) is shown in Fig. 4.
Embodiment 16
According to each Step By Condition of embodiment 13, but during dispensing, feed molar proportioning is with Al2O3、SiO2、P2O5、
H2O, R meter is changed to Al2O3:0.4SiO2:P2O5:50H2O:4.1DIPEA, and the pressure release scope during pressure discharge operations is changed to
30%, the SAPO-18 zeolite product yield finally obtaining is 92%, and degree of crystallinity is 153%.The X-ray diffraction of gained sample
Spectrogram (XRD) is shown in Fig. 4.
All comparative examples and actual pressure discharge operations condition, the yield of products obtained therefrom and relative crystallinity and the hydro-thermal of embodiment
Stability test result is all listed in table 1.
Table 1
Claims (12)
1. a kind of preparation method of crystalline state SAPO material is it is characterised 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, then by ball milling
Molecular screen primary powder afterwards is added in inorganic acid solution, activation processing at a temperature of 60～120 DEG C, that is, obtain seed-solution；
(2) phosphorus source, silicon source, silicon source, organic formwork agent R and deionized water are added in autoclave and prepare before Crystallization of Zeolite
Colloid solution, is subsequently adding seed-solution, through stirring mixing, at first crystallization under 130～220 DEG C, self-generated pressure
Reason 1～24 hour；
(3) under hot conditionss, a certain degree of pressure discharge operations are carried out to synthesis reaction kettle body system in the original location, be then shut off and seal
Autoclave, Crystallizing treatment temperature be 130～220 DEG C and Crystallizing treatment time be 2～60 little at present, at further crystallization
Reason, obtains crystalline state SAPO material；
Mineral acid in described step (1) includes phosphoric acid, hydrochloric acid, nitric acid, one of sulphuric acid or arbitrarily several mixture,
The mass percent concentration of inorganic acid solution is 0.05%～5%；
The mol ratio of each material adding during colloid solution before preparing Crystallization of Zeolite in described step (2) forms with Al2O3、
SiO2、P2O5、H2O, R are calculated as Al2O3:aSiO2:bP2O5:cH2O:DR, wherein R are organic formwork agent, and the scope of a is 0.05～2,
The scope for 0.5～3, c for the scope of b is the scope of 10～200, d is 0.5～6；
The pressure release scope of the pressure discharge operations part in described step (3) is self-generated pressure in the reactor under crystallization temperature
5%～30%.
2. method according to claim 1 is it is characterised in that the mineral acid in step (1) for mass percent concentration is
0.3%～1.5% phosphoric acid solution.
3. method according to claim 1 is it is characterised in that activating treatment temperature in step (1) is 70～110 DEG C,
Process time is 1～12 hour.
4. method according to claim 1 it is characterised in that the phosphorus source in step (2) include orthophosphoric acid, ammonium hydrogen phosphate,
One of ammonium dihydrogen phosphate, organic phosphorus compound or phosphorous oxides or arbitrarily several mixture.
5. method according to claim 1 is it is characterised in that the silicon source in step (2) includes boehmite, isopropanol
One of aluminum, aluminium salt, hydrated alumina, aluminum alkoxide, Alumina gel, activated alumina or arbitrarily several mixture.
6. method according to claim 1 is it is characterised in that the silicon source in step (2) includes Ludox, reactive silica
One of silicon, positive esters of silicon acis or arbitrarily several mixture.
7. it is characterised in that the phosphorus source in step (2) is orthophosphoric acid, silicon source is that silicon is molten to method according to claim 1
Glue, silicon source is boehmite.
8. method according to claim 1 it is characterised in that the organic formwork agent R in step (2) include triethylamine, two
Ethamine, di-n-propylamine, diisopropylamine, morpholine, N, one of N- diisopropylethylamine, tetraethyl ammonium hydroxide or arbitrarily several
Mixture.
9. method according to claim 1 is it is characterised in that the pressure release scope of pressure discharge operations part in step (3) is
The 0.1～40% of self-generated pressure in reactor under crystallization temperature.
10. method according to claim 1 is it is characterised in that the gas that the pressure discharge operations in step (3) are discharged is carried out
Condensation recycle and reuse.
11. methods according to claim 1 it is characterised in that step (1), step (2), step (3) building-up process equal
Carry out under continuous stirring or rotation.
12. methods according to claim 1 are it is characterised in that the described crystalline state SAPO material that obtains is phosphoric acid
Si-Al molecular sieve material, including SAPO-5, SAPO-11, SAPO-18 and SAPO-34.
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| CN105964295B (en) * | 2016-05-24 | 2019-01-18 | 华南理工大学 | A kind of the Mn-SAPO-34 molecular sieve catalyst and preparation method thereof and purposes of richness manganese |
| CN105944756B (en) * | 2016-05-24 | 2019-01-29 | 华南理工大学 | A kind of MnCu-SAPO-34 molecular sieve catalyst and preparation method thereof and purposes |
| CN109133092A (en) * | 2017-06-27 | 2019-01-04 | 中国石油化工股份有限公司 | A method of preparing molecular sieve |
| CN109796028B (en) * | 2017-11-17 | 2020-10-27 | 神华集团有限责任公司 | Method for preparing silicoaluminophosphate molecular sieve, silicoaluminophosphate molecular sieve and method for preparing olefin from methanol |
| CN109437225A (en) * | 2018-12-06 | 2019-03-08 | 复榆(张家港)新材料科技有限公司 | A kind of synthetic method and device of silica-rich zeolite molecular sieve |
| CN109761243A (en) * | 2019-02-21 | 2019-05-17 | 正大能源材料(大连)有限公司 | A kind of preparation of low silicon small grain SAPO-34 molecular sieve and application method |
| 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 |
| CN113620312B (en) * | 2021-08-24 | 2023-02-03 | 常州工学院 | Preparation method of SAPO-20 zeolite molecular sieve with high crystallinity |
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