CN103553077B - A kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous - Google Patents
A kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous Download PDFInfo
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Abstract
Have a synthetic method for the SAPO-31 molecular sieve of multi-stage porous, it relates to the synthetic method of SAPO-31 molecular sieve.The present invention will solve the method for existing synthesis SAPO-31 molecular sieve without mesopore orbit, and diffusion is poor, makes the problem that it is restricted as the application of catalyzer.Method: one, prepare Primogel; Two, crystallization and roasting, the i.e. obtained SAPO-31 molecular sieve with multi-stage porous.SAPO-31 molecular sieve prepared by the present invention has micropore and mesopore orbit simultaneously, greatly enhance the diffusion in this molecular sieve pore passage of reactant and product and conversion capability, improve its catalytic activity and the selectivity to target product, in the catalysis of fine chemistry industry, petrochemical complex, absorption with in being separated, there is very important using value.The method is a kind of eco-friendly method, simple to operate, is easy to accomplish scale production.
Description
Technical field
The present invention relates to the synthetic method of SAPO-31 molecular sieve.
Background technology
The SAPO-31 molecular sieve with circular one dimension non-crossing straight hole road not only has suitable pore passage structure and size (0.54nm × 0.54nm), and there is gentleer acidity, acid carrier as normal paraffin hygrogenating isomerization reaction is more conducive to generation and the diffusion of single branched chain isomer, therefore, SAPO-31 molecular sieve to coagulate at the hydroisomerizing of fraction oil of petroleum as the acid carrier of dual-function catalyst and to close and isomerization dewaxing produces in the production of high product matter Chai oil and low condensation point lubricating oil the isomerisation selectivity shown than zeolite molecular sieve and the higher catalytic stability of other silicon aluminium phosphate molecular sieve analogs and Geng Gao, have broad application prospects in refining of petroleum and field of petrochemical industry.
In the molecular sieve with hierarchical porous structure, owing to having constructed mesoporous passage between micropore canals, shorten the journey spacing of reactant and product diffusion and the residence time in duct, reactant and the macromolecular diffusion of product can be improved significantly, therefore molecular sieve can and acidic site more, the transformation efficiency of reactant can be significantly improved as catalyzer, improve the selectivity of Primary product.
Sour dealuminzation is carried out to the molecular sieve of synthesis, alkali desiliconization modification can remove aluminium in zeolite molecular sieve skeleton or Siliciumatom, form a large amount of rooms, and the appearance in room can cause the breakpoint in molecular sieve structure grid to occur, make the mutual UNICOM of a part of aperture and form secondary mesopore.Although multi-stage porous molecular sieve can be formed in this way, but the degree of dealuminzation or desiliconization is difficult to grasp, the amount increase that skeletal atom removes is easy to cause the skeleton of zeolite molecular sieve to subside, and the aluminium removed or silicon species also may block duct or the aperture of molecular sieve, therefore poor by the acid and alkali-resistance ability of the molecular sieve of dealuminzation, desiliconization modification.
In sum, the pore size little (0.54nm × 0.54nm) of the micropore SAPO-31 molecular sieve of existing method synthesis, limit reactant and the diffusion of product in its duct, and there is modification degree problem very rambunctious by the method for dealuminzation or desiliconization modification formation mesopore orbit, and the amount increase that skeletal atom removes is easy to cause the skeleton of zeolite molecular sieve to subside, the aluminium removed or silicon species also may block duct or the aperture of molecular sieve, therefore, pass through dealuminzation, it is poor to there is acid and alkali-resistance ability in multi-stage porous molecular sieve prepared by desiliconization modification, complex operation, the series of problems such as not easily to implement and environment is unfriendly.
Summary of the invention
There is not mesopore orbit in the method that the present invention will solve existing synthesis SAPO-31 molecular sieve, the acid and alkali-resistance ability of the molecular sieve adopting two-step fabrication to prepare is poor, complex operation, not easily enforcement and the disagreeableness problem of environment, and provides a kind of double-template method of micropore template and mesoporous template that adopts to synthesize the method with the SAPO-31 molecular sieve of multi-stage porous.
There is a synthetic method for the SAPO-31 molecular sieve of multi-stage porous, specifically carry out according to following steps:
One, Primogel is prepared: take phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and deionized water and mix, mesoporous template is added again in this mixture, then the mixture adding mesoporous template is stirred 3h ~ 8h under rotating speed is 600r/min ~ 1200r/min, obtain Primogel;
Described phosphoric acid and the mass ratio of pseudo-boehmite are 1:(0.40 ~ 0.80); Described phosphoric acid and the mass ratio of silicon sol are 1:(0.30 ~ 0.90); Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:(0.20 ~ 0.90); Described phosphoric acid and the mass ratio of deionized water are 1:(2.00 ~ 4.00); The mass ratio of described phosphoric acid and mesoporous template is 1:(0.05 ~ 0.40);
Two, crystallization and roasting: Primogel is placed in band teflon-lined stainless steel crystallizing kettle, crystallization 12h ~ 60h at temperature is 170 DEG C ~ 190 DEG C, crystallization product is cooled to room temperature, again through centrifugation and washing, and at temperature is 100 DEG C ~ 120 DEG C dry 10h ~ 24h, finally dried crystallization product is placed in retort furnace, roasting 6h ~ 8h at temperature is 500 DEG C ~ 700 DEG C, the obtained SAPO-31 molecular sieve with multi-stage porous.
The invention has the beneficial effects as follows: the duct characteristic one, effectively improving molecular sieve, mesopore orbit size is within the scope of 5 ~ 30nm, therefore, prepare in the technique of low-freezing lubricating oil at lubricating oil isomerization dewaxing, reactant and product fully can spread in mesoporous, thus improve the selectivity of band branched chain isomer alkane; Two, the present invention is by first making Primogel, successfully synthesized by conventional hydrothermal method again and there is micropore and mesoporous multi-stage porous SAPO-31 molecular sieve simultaneously, avoid the problems such as the method using sour dealuminzation and alkali desiliconization etc. to form mesopore orbit may cause that framework of molecular sieve subsides, therefore, effectively improve the acid and alkali-resistance ability of molecular sieve, the acid carrier that can be used as an acidic catalyst or dual-function catalyst is applied in the fields such as refining of petroleum, petrochemical complex, basic organic chemical industry and fine chemistry industry; Three, avoid the method using sour dealuminzation and alkali desiliconization, decreasing environmental pollution, is eco-friendly method; Four, synthetic method is simple to operate, is easy to accomplish scale production.
The present invention is used for a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous.
Accompanying drawing explanation
Fig. 1 is SAPO-31 molecular sieve X ray diffracting spectrum prepared by embodiment one;
Fig. 2 is SAPO-31 molecular sieve scanning electron microscope diagram prepared by embodiment one;
Fig. 3 is SAPO-31 molecular sieve transmission electron microscope figure prepared by embodiment one;
Fig. 4 is SAPO-31 molecular sieve N prepared by embodiment one
2physical adsorption figure;
Fig. 5 is SAPO-31 molecular sieve bore diameter distribution plan prepared by embodiment one;
Fig. 6 is SAPO-31 molecular sieve X ray diffracting spectrum prepared by embodiment two;
Fig. 7 is SAPO-31 molecular sieve scanning electron microscope diagram prepared by embodiment two;
Fig. 8 is SAPO-31 molecular sieve transmission electron microscope figure prepared by embodiment two;
Fig. 9 is SAPO-31 molecular sieve N prepared by embodiment two
2physical adsorption figure;
Figure 10 is SAPO-31 molecular sieve bore diameter distribution plan prepared by embodiment two;
Figure 11 is SAPO-31 molecular sieve X ray diffracting spectrum prepared by embodiment three;
Figure 12 is SAPO-31 molecular sieve scanning electron microscope diagram prepared by embodiment three;
Figure 13 is SAPO-31 molecular sieve transmission electron microscope figure prepared by embodiment three;
Figure 14 is SAPO-31 molecular sieve N prepared by embodiment three
2physical adsorption figure;
Figure 15 is SAPO-31 molecular sieve bore diameter distribution plan prepared by embodiment three.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous described in present embodiment, specifically carry out according to following steps:
One, Primogel is prepared: take phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and deionized water and mix, mesoporous template is added again in this mixture, then the mixture adding mesoporous template is stirred 3h ~ 8h under rotating speed is 600r/min ~ 1200r/min, obtain Primogel;
Described phosphoric acid and the mass ratio of pseudo-boehmite are 1:(0.40 ~ 0.80); Described phosphoric acid and the mass ratio of silicon sol are 1:(0.30 ~ 0.90); Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:(0.20 ~ 0.90); Described phosphoric acid and the mass ratio of deionized water are 1:(2.00 ~ 4.00); The mass ratio of described phosphoric acid and mesoporous template is 1:(0.05 ~ 0.40);
Two, crystallization and roasting: Primogel is placed in band teflon-lined stainless steel crystallizing kettle, crystallization 12h ~ 60h at temperature is 170 DEG C ~ 190 DEG C, crystallization product is cooled to room temperature, again through centrifugation and washing, and at temperature is 100 DEG C ~ 120 DEG C dry 10h ~ 24h, finally dried crystallization product is placed in retort furnace, roasting 6h ~ 8h at temperature is 500 DEG C ~ 700 DEG C, the obtained SAPO-31 molecular sieve with multi-stage porous.
The beneficial effect of present embodiment is: the duct characteristic one, effectively improving molecular sieve, mesopore orbit size is within the scope of 5 ~ 30nm, therefore, to prepare at lubricating oil isomerization dewaxing as the acid carrier of dual-function catalyst in the technique of low-freezing lubricating oil can effectively improve reactant and product in duct in diffusion, thus improve the selectivity of branched isoparaffin; Two, the present invention is by first making Primogel, successfully synthesized by conventional hydrothermal method again and there is micropore and mesoporous multi-stage porous SAPO-31 molecular sieve simultaneously, avoid the problem using sour dealuminzation and alkali desiliconization to cause framework of molecular sieve to subside to the method that micro porous molecular sieve modification produces secondary mesopore, therefore, effectively improve the acid and alkali-resistance ability of molecular sieve, the acid carrier that can be used as an acidic catalyst or dual-function catalyst is applied in the fields such as refining of petroleum, petrochemical complex, basic organic chemical industry and fine chemistry industry; Three, avoiding the problem of environmental pollution using the method for sour dealuminzation and alkali desiliconization generation secondary mesopore to bring, is a kind of environment-friendly method; Four, synthetic method is simple to operate, is easy to accomplish scale production.
Embodiment two: present embodiment and embodiment one unlike: the mass percentage of the phosphoric acid described in step one is 85%; Al in pseudo-boehmite described in step one
2o
3massfraction be 71.13%; SiO in silicon sol described in step one
2massfraction be 26.85%; The mass percentage of the Di-n-Butyl Amine described in step one is 95.00%.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two unlike: the mass ratio of the phosphoric acid described in step one and pseudo-boehmite is 1:(0.50 ~ 0.70); Described phosphoric acid and the mass ratio of silicon sol are 1:(0.40 ~ 0.80); Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:(0.30 ~ 0.70); Described phosphoric acid and the mass ratio of deionized water are 1:(2.50 ~ 3.50); The mass ratio of described phosphoric acid and mesoporous template is 1:(0.05 ~ 0.35).Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the mass ratio of the phosphoric acid described in step one and pseudo-boehmite is 1:0.60; Described phosphoric acid and the mass ratio of silicon sol are 1:(0.40 ~ 0.80); Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:0.80; Described phosphoric acid and the mass ratio of deionized water are 1:3.00; The mass ratio of described phosphoric acid and mesoporous template is 1:(0.05 ~ 0.2).Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: mesoporous template described in step one is dodecyl dimethyl trimethoxy silicon propyl ammonium chloride, dodecyldimethylamine base trimethoxy silicon propyl ammonium chloride, hexadecyldimethyl benzyl ammonium trimethoxy silicon propyl ammonium chloride, octadecyldimethyl trimethoxy silicon propyl ammonium chloride, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, polyethylene oxide-propyleneoxide-ethyleneoxide triblock copolymer, glucose or sucrose.Other is identical with embodiment one to four.
Embodiment six: present embodiment and one of embodiment one to five unlike: take phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and deionized water in step one and mix, mesoporous template is added again in this mixture, then the mixture adding mesoporous template is stirred 4h under rotating speed is 800r/min, obtain Primogel.Other is identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: in step 2, Primogel is placed in band teflon-lined stainless steel crystallizing kettle crystallization 12h ~ 48h at temperature is 170 DEG C ~ 190 DEG C, and crystallization product is cooled to room temperature.Other is identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: in step 2, crystallization product is cooled to through centrifugation and washing after room temperature, and at temperature is 100 DEG C ~ 120 DEG C dry 12h.Other is identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: in step 2, dried crystallization product is placed in retort furnace roasting 6h at temperature is 500 DEG C ~ 700 DEG C, the obtained SAPO-31 molecular sieve with multi-stage porous.Other is identical with embodiment one to eight.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
A kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous described in the present embodiment, specifically carry out according to following steps:
One, Primogel is prepared: take phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and deionized water and mix, mesoporous template is added again in this mixture, then the mixture adding mesoporous template is stirred 4h under rotating speed is 800r/min, obtain Primogel;
The mass percentage of described phosphoric acid is 85%; Al in described pseudo-boehmite
2o
3massfraction be 71.13%; SiO in described silicon sol
2massfraction be 26.85%; The mass percentage of described Di-n-Butyl Amine is 95.00%; Described mesoporous template is hexadecyldimethyl benzyl ammonium trimethoxy silicon propyl ammonium chloride; Described phosphoric acid and the mass ratio of pseudo-boehmite are 1:0.60; Described phosphoric acid and the mass ratio of silicon sol are 1:0.60; Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:0.80; Described phosphoric acid and the mass ratio of deionized water are 1:3.00; The mass ratio of described phosphoric acid and mesoporous template is 1:0.11;
Two, crystallization and roasting: Primogel is placed in band teflon-lined stainless steel crystallizing kettle, crystallization 24h at temperature is 185 DEG C, crystallization product is cooled to room temperature, again through centrifugation and washing, and at temperature is 110 DEG C dry 12h, finally dried crystallization product is placed in retort furnace, roasting 6h at temperature is 600 DEG C, the obtained SAPO-31 molecular sieve with multi-stage porous.
SAPO-31 molecular sieve X ray diffracting spectrum prepared by the present embodiment as shown in Figure 1, as seen from the figure, is 8.5 ° at 2 θ, 20.2 °, locates the characteristic diffraction peak all occurring SAPO-31 molecular sieve for 22.0 ° and 22.5 °, and without other stray crystal.
As shown in Figure 2, as seen from the figure, SAPO-31 molecular sieve prepared by the present embodiment is the aggregate of irregular cubic grain to SAPO-31 molecular sieve scanning electron microscope diagram prepared by the present embodiment.
As shown in Figure 3, as seen from the figure, the mesopore orbit of SAPO-31 molecular sieve prepared by the present embodiment is of a size of 5nm ~ 30nm to SAPO-31 molecular sieve transmission electron microscope figure prepared by the present embodiment.
SAPO-31 molecule N prepared by the present embodiment
2physical adsorption figure as shown in Figure 4, as seen from the figure, the N of SAPO-31 molecular sieve prepared by the present embodiment
2adsorption-desorption isothermal has back stagnant ring.
As shown in Figure 5, as seen from the figure, SAPO-31 molecular sieve prepared by the present embodiment has micropore and mesoporous hierarchical porous structure to SAPO-31 molecule graph of pore diameter distribution prepared by the present embodiment, and mesoporous pore size is distributed within the scope of 5nm ~ 30nm.
Embodiment two:
A kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous described in the present embodiment, specifically carry out according to following steps:
One, Primogel is prepared: take phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and deionized water and mix, mesoporous template is added again in this mixture, then the mixture adding mesoporous template is stirred 4h under rotating speed is 800r/min, obtain Primogel;
The mass percentage of described phosphoric acid is 85%; Al in described pseudo-boehmite
2o
3massfraction be 71.13%; SiO in described silicon sol
2massfraction be 26.85%; The mass percentage of described Di-n-Butyl Amine is 95.00%; Described mesoporous template is polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer; Described phosphoric acid and the mass ratio of pseudo-boehmite are 1:0.60; Described phosphoric acid and the mass ratio of silicon sol are 1:0.60; Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:0.80; Described phosphoric acid and the mass ratio of deionized water are 1:3.00; The mass ratio of described phosphoric acid and mesoporous template is 1:0.11;
Two, crystallization and roasting: Primogel is placed in band teflon-lined stainless steel crystallizing kettle, crystallization 24h at temperature is 185 DEG C, crystallization product is cooled to room temperature, again through centrifugation and washing, and at temperature is 110 DEG C dry 12h, finally dried crystallization product is placed in retort furnace, roasting 6h at temperature is 600 DEG C, the obtained SAPO-31 molecular sieve with multi-stage porous.
SAPO-31 molecular sieve X ray diffracting spectrum prepared by the present embodiment as shown in Figure 6, as seen from the figure, is 8.5 ° at 2 θ, 20.2 °, locates the characteristic diffraction peak all occurring SAPO-31 molecular sieve for 22.0 ° and 22.5 °, and without other stray crystal.
SAPO-31 molecular sieve scanning electron microscope diagram prepared by the present embodiment as shown in Figure 7, as seen from the figure, the tufted aggregate that SAPO-31 molecular sieve prepared by the present embodiment is assembled by little crystal grain.
As shown in Figure 8, as seen from the figure, the mesopore orbit size of SAPO-31 molecular sieve prepared by the present embodiment is mainly about 10nm to SAPO-31 molecular sieve transmission electron microscope prepared by the present embodiment.
SAPO-31 molecule N prepared by the present embodiment
2physical adsorption figure as shown in Figure 9, as seen from the figure, the N of SAPO-31 molecular sieve prepared by the present embodiment
2adsorption-desorption isothermal has back stagnant ring.
As shown in Figure 10, as seen from the figure, SAPO-31 molecular sieve prepared by the present embodiment has micropore and mesoporous hierarchical porous structure to SAPO-31 molecule graph of pore diameter distribution prepared by the present embodiment, and mesoporous pore size is distributed within the scope of 5nm ~ 30nm.
Embodiment three:
A kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous described in the present embodiment, specifically carry out according to following steps:
One, Primogel is prepared: take phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and deionized water and mix, mesoporous template is added again in this mixture, then the mixture adding mesoporous template is stirred 4h under rotating speed is 800r/min, obtain Primogel;
The mass percentage of described phosphoric acid is 85%; Al in described pseudo-boehmite
2o
3massfraction be 71.13%; SiO in described silicon sol
2massfraction be 26.85%; The mass percentage of described Di-n-Butyl Amine is 95.00%; Described mesoporous template is glucose; Described phosphoric acid and the mass ratio of pseudo-boehmite are 1:0.60; Described phosphoric acid and the mass ratio of silicon sol are 1:0.60; Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:0.80; Described phosphoric acid and the mass ratio of deionized water are 1:3.00; The mass ratio of described phosphoric acid and mesoporous template is 1:0.11;
Two, crystallization and roasting: Primogel is placed in band teflon-lined stainless steel crystallizing kettle, crystallization 24h at temperature is 185 DEG C, crystallization product is cooled to room temperature, again through centrifugation and washing, and at temperature is 110 DEG C dry 12h, finally dried crystallization product is placed in retort furnace, roasting 6h at temperature is 600 DEG C, the obtained SAPO-31 molecular sieve with multi-stage porous.
SAPO-31 molecular sieve X ray diffracting spectrum prepared by the present embodiment as shown in figure 11, as seen from the figure, is 8.5 ° at 2 θ, 20.2 °, locates the characteristic diffraction peak all occurring SAPO-31 molecular sieve for 22.0 ° and 22.5 °, and without other stray crystal.
SAPO-31 molecular sieve scanning electron microscope diagram prepared by the present embodiment as shown in figure 12, as seen from the figure, the dumbbell shaped aggregate that SAPO-31 molecular sieve prepared by the present embodiment is assembled by little crystal grain.
As shown in figure 13, as seen from the figure, the mesopore orbit of SAPO-31 molecular sieve prepared by the present embodiment is of a size of 5nm ~ 17nm to SAPO-31 molecular sieve transmission electron microscope figure prepared by the present embodiment.
SAPO-31 molecule N prepared by the present embodiment
2physical adsorption figure as shown in figure 14, as seen from the figure, the N of SAPO-31 molecular sieve prepared by the present embodiment
2adsorption-desorption isothermal has back stagnant ring.
As shown in figure 15, as seen from the figure, SAPO-31 molecular sieve prepared by the present embodiment has micropore and mesoporous hierarchical porous structure to SAPO-31 molecule graph of pore diameter distribution prepared by the present embodiment, and mesoporous pore size is distributed within the scope of 5nm ~ 17nm.
Claims (8)
1. there is a synthetic method for the SAPO-31 molecular sieve of multi-stage porous, it is characterized in that a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous is carried out according to following steps:
One, Primogel is prepared: take phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and deionized water and mix, mesoporous template is added again in this mixture, then the mixture adding mesoporous template is stirred 3h ~ 8h under rotating speed is 600r/min ~ 1200r/min, obtain Primogel;
Described phosphoric acid and the mass ratio of pseudo-boehmite are 1:(0.40 ~ 0.80); Described phosphoric acid and the mass ratio of silicon sol are 1:(0.30 ~ 0.90); Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:(0.20 ~ 0.90); Described phosphoric acid and the mass ratio of deionized water are 1:(2.00 ~ 4.00); The mass ratio of described phosphoric acid and mesoporous template is 1:(0.05 ~ 0.40);
Described mesoporous template is dodecyl dimethyl trimethoxy silicon propyl ammonium chloride, dodecyldimethylamine base trimethoxy silicon propyl ammonium chloride, octadecyldimethyl trimethoxy silicon propyl ammonium chloride, polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, polyethylene oxide-propyleneoxide-ethyleneoxide triblock copolymer or sucrose;
Two, crystallization and roasting: Primogel is placed in band teflon-lined stainless steel crystallizing kettle, crystallization 12h ~ 60h at temperature is 170 DEG C ~ 190 DEG C, crystallization product is cooled to room temperature, again through centrifugation and washing, and at temperature is 100 DEG C ~ 120 DEG C dry 10h ~ 24h, finally dried crystallization product is placed in retort furnace, roasting 6h ~ 8h at temperature is 500 DEG C ~ 700 DEG C, the obtained SAPO-31 molecular sieve with multi-stage porous.
2. a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous according to claim 1, is characterized in that the mass percentage of the phosphoric acid described in step one is 85%; Al in pseudo-boehmite described in step one
2o
3massfraction be 71.13%; SiO in silicon sol described in step one
2massfraction be 26.85%; The mass percentage of the Di-n-Butyl Amine described in step one is 95.00%.
3. a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous according to claim 1, is characterized in that the mass ratio of the phosphoric acid described in step one and pseudo-boehmite is 1:(0.50 ~ 0.70); Described phosphoric acid and the mass ratio of silicon sol are 1:(0.40 ~ 0.80); Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:(0.30 ~ 0.70); Described phosphoric acid and the mass ratio of deionized water are 1:(2.50 ~ 3.50); The mass ratio of described phosphoric acid and mesoporous template is 1:(0.05 ~ 0.35).
4. a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous according to claim 1, is characterized in that the mass ratio of the phosphoric acid described in step one and pseudo-boehmite is 1:0.60; Described phosphoric acid and the mass ratio of silicon sol are 1:(0.40 ~ 0.80); Described phosphoric acid and the mass ratio of Di-n-Butyl Amine are 1:0.80; Described phosphoric acid and the mass ratio of deionized water are 1:3.00; The mass ratio of described phosphoric acid and mesoporous template is 1:(0.05 ~ 0.2).
5. a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous according to claim 1, it is characterized in that taking phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and deionized water in step one and mixing, mesoporous template is added again in this mixture, then the mixture adding mesoporous template is stirred 4h under rotating speed is 800r/min, obtain Primogel.
6. a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous according to claim 1, it is characterized in that in step 2, Primogel being placed in band teflon-lined stainless steel crystallizing kettle, at temperature is 170 DEG C ~ 190 DEG C after crystallization 12h ~ 48h, crystallization product is cooled to room temperature.
7. a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous according to claim 1, is characterized in that being cooled to by crystallization product in step 2 through centrifugation and washing after room temperature, and at temperature is 100 DEG C ~ 120 DEG C dry 12h.
8. a kind of synthetic method with the SAPO-31 molecular sieve of multi-stage porous according to claim 1, it is characterized in that, in step 2, dried crystallization product is placed in retort furnace, roasting 6h at temperature is 500 DEG C ~ 700 DEG C, the obtained SAPO-31 molecular sieve with multi-stage porous.
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| CN110304984B (en) * | 2019-08-13 | 2022-03-15 | 黑龙江大学 | Method for preparing isohexadecane by using bifunctional catalyst |
| CN110407232B (en) * | 2019-08-13 | 2023-06-27 | 黑龙江大学 | Synthesis method of hierarchical pore SAPO-41 molecular sieve nanosheets |
| CN112723380A (en) * | 2020-12-24 | 2021-04-30 | 西安科技大学 | Method for preparing hierarchical pore SAPO-20 molecular sieve from illite |
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