CN113860328B - SAPO-17 molecular sieve, and preparation method and application thereof - Google Patents

SAPO-17 molecular sieve, and preparation method and application thereof Download PDF

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CN113860328B
CN113860328B CN202111294606.7A CN202111294606A CN113860328B CN 113860328 B CN113860328 B CN 113860328B CN 202111294606 A CN202111294606 A CN 202111294606A CN 113860328 B CN113860328 B CN 113860328B
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CN113860328A (en
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宋晓伟
王超然
李晓
梁志强
于吉红
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Jilin University
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Abstract

The invention provides an SAPO-17 molecular sieve, a preparation method and an application thereof, belonging to the technical field of chemical adsorbents. The method disclosed by the invention is used for crystallizing under the microwave condition, is uniformly heated and has a high heating speed, and meanwhile, the crystal seeds are added, so that crystal nuclei are easily formed on the surfaces of the crystal seed structural fragments, and the synergistic effect of the microwave and the crystal seeds is utilized to be more favorable for the rapid growth of crystals, so that the SAPO-17 molecular sieve with high crystallinity and good stability is obtained. The method adopts the seed crystal and microwave assisted method to quickly synthesize the SAPO-17 molecular sieve, can shorten the crystallization time (1-10 min), and the prepared molecular sieve has higher specific surface area and pore volume and has higher specific surface area and pore volume with CO 2 Has stronger interaction force and thus higher CO 2 Adsorption capacity to CO 2 Has better selective adsorption, thereby having better CO adsorption 2 And N 2 Has high adsorption and separation effect.

Description

SAPO-17 molecular sieve, and preparation method and application thereof
Technical Field
The invention relates to the technical field of chemical adsorbents, and particularly relates to a SAPO-17 molecular sieve and a preparation method and application thereof.
Background
The SAPO-ERI molecular sieve with the ERI type framework structure belongs to 8-membered ring small-pore zeolite, has unique micropores and a huge super cage structure, and is concerned about the fields of adsorption separation, removal of nitrogen oxides, preparation of olefins from methanol and the like.
The pure ERI type zeolite has higher synthesis difficulty and is easy to generate the symbiotic zeolite with OFF type framework structure zeolite. The synthesis of the pure SAPO-17 molecular sieve usually crystallizes for 3 to 4 days under the hydrothermal condition, so that the energy consumption is large and the synthesis cost is high. Wang et al (Wang Yapei, xu Jun, zhang Xiaoxiao, etc.. Rapid and Stable Synthesis and characterization of SAPO-17 molecular sieves in HF and KCl containing systems [ J ]. Modernization chemical, 2018,38,159-163) can obtain pure phase SAPO-17 molecular sieves in 3h at the fastest speed by adding hydrofluoric acid and inorganic salt potassium chloride. Zhong (ZHONG S, SONG S, WANG B, et al fast prediction of ERI-structure AlPO-17 and SAPO-17 in the presentation of isophorous and xenogeneous feeds [ J ]. Microporus and meso Materials,2018,263,11-20) et al also accelerated the synthesis of SAPO-17 molecular sieves by introducing a silicon precursor (type T molecular sieves) to obtain pure phase SAPO-17 molecular sieves at 2.5h at the fastest speed.
The aluminosilicate molecular sieve has stronger basic sites, so the aluminosilicate molecular sieve has stronger CO 2 Adsorption capacity; however, due to CO 2 Has stronger acting force with alkaline sites, so the desorption is not facilitated under certain conditions, and the cyclic utilization of the organic acid in the industrial field is limited. Conventional SAPO-17 molecular sieves typically exhibit on CO 2 The CO has stronger affinity but is influenced by the reason that the synthetic crystallinity is not high and the like 2 /N 2 And (4) adsorption separation effect.
Disclosure of Invention
The invention aims to provide an SAPO-17 molecular sieve and a preparation method and application thereof, and the prepared SAPO-17 molecular sieve has high crystallinity and is resistant to CO 2 And N 2 Has high adsorption and separation effect.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an SAPO-17 molecular sieve, which comprises the following steps:
mixing phosphoric acid, an aluminum source, a silicon source, a template agent and water, and aging to obtain an aged product;
mixing the aged product with SAPO-17-180 molecular sieve crystal seeds, and gelatinizing to obtain gel;
crystallizing the gel under the microwave condition to obtain a crystallized product;
and calcining the crystallized product to obtain the SAPO-17 molecular sieve.
Preferably, the silicon source is one or more of Ludox-AS, ethyl orthosilicate and silica sol; the aluminum source is one or more of pseudo-boehmite, aluminum isopropoxide and aluminum nitrate; the template agent is cyclohexylamine, quinuclidine or N, N, N ', N' -tetramethyl-1,6-hexanediamine.
Preferably, the silicon source, the aluminum source and the phosphoric acid are respectively in SiO 2 、Al 2 O 3 And P 2 O 5 The molar ratio of the template agent, the silicon source, the aluminum source, the phosphoric acid and the water is (0.8-3): (0.1-0.4): (0.4-2.0): (0.8-1.0): (30-60).
Preferably, the aging temperature is 60-100 ℃, and the aging time is 10-30 h.
Preferably, the silicon source, the aluminum source and the phosphoric acid are respectively in SiO 2 、Al 2 O 3 And P 2 O 5 The mass ratio of the mass of the SAPO-17-180 molecular sieve seed crystal to the total mass of the silicon source, the aluminum source and the phosphoric acid is (0.05-0.1): 1.
Preferably, the microwave condition is provided by a microwave reactor, and the temperature rise program of the microwave reactor is to raise the temperature to 160-250 ℃ within 3-10 min, and the power is 280-300W.
Preferably, the crystallization temperature is 160-250 ℃ and the crystallization time is 1-180 min.
Preferably, the calcining temperature is 550-700 ℃ and the calcining time is 4-8 h.
The invention provides the SAPO-17 molecular sieve prepared by the preparation method in the technical scheme, wherein the SAPO-17 molecular sieve is in a hexagonal prism shape, and the side length of the hexagonal prism shape is 0.66 mu m multiplied by 0.26 mu m.
The invention provides the technical scheme that the SAPO-17 molecular sieve is used as CO 2 The application of the adsorbent.
The invention provides a preparation method of an SAPO-17 molecular sieve, which comprises the following steps: mixing phosphoric acid, an aluminum source, a silicon source, a template agent and water, and aging to obtain an aged product; mixing the aged product with SAPO-17-180 molecular sieve crystal seeds, and gelling to obtain gel; crystallizing the gel under the microwave condition to obtain a crystallized product; and calcining the crystallized product to obtain the SAPO-17 molecular sieve. The method is used for crystallization under the microwave condition, is uniformly heated and has high heating speed, and crystal seeds are added, so that crystal nuclei are easily formed on the surfaces of crystal seed structure fragments, and the synergistic effect of the microwave and the crystal seeds is utilized to accelerate the crystallization process, so that the higher the crystallization rate in a specified time, the higher the crystallization degree can be, the more the rapid growth of crystals is facilitated, and the SAPO-17 molecular sieve with high crystallinity, good stability and larger specific surface area and pore volume is obtained.
In addition, after the seed crystal is added, the competitive growth among the crystal cores reduces the grain size, and the CO of the SAPO-17 molecular sieve with smaller size 2 The adsorption capacity is obviously increased, and the cost is saved.
The method adopts the seed crystal and microwave assisted method to quickly synthesize the SAPO-17 molecular sieve, can shorten the crystallization time (1-10 min), and the prepared molecular sieve has high crystallinity, good stability, high specific surface area and pore volume, and high specific surface area and pore volume compared with CO 2 Has stronger interaction force and thus higher CO 2 Adsorption capacity to CO 2 Has better selective adsorption, thereby having better CO adsorption 2 And N 2 Has high adsorption and separation effect.
The method disclosed by the invention has the advantages that the SAPO-17 molecular sieve is quickly synthesized by using the crystal seed and microwave assisted method, the synthesis period is short, the repeatability is good, the synthesis time consumption of the SAPO-17 molecular sieve material is effectively reduced, and the problems of long synthesis period (the synthesis is crystallized for 3-4 days under the hydrothermal condition), high cost and complex synthesis process of the traditional SAPO-17 molecular sieve are solved.
Drawings
FIG. 1 is an XRD pattern of samples prepared with SAPO-17 in example 1 and comparative example 3 prepared at different crystallization times;
FIG. 2 is an SEM image of SAPO-17 molecular sieves prepared in example 1 at different crystallization times;
FIG. 3 is an XRD pattern of a sample prepared in comparative example 1 at different crystallization times and an XRD pattern of a sample prepared in comparative example 2;
FIG. 4 is an SEM image of seed SAPO-17-180 and SAPO-17-30, prepared as in comparative example 1;
FIG. 5 is a graph showing CO for SAPO-17-seed-1 prepared in example 1 and SAPO-17-30 prepared in comparative example 1 2 And N 2 Adsorption/desorption diagram, CO 2 /N 2 An adsorption separation curve graph and an adsorption heat curve graph;
FIG. 6 shows SAPO-17-30 and SAPO-17-180 as prepared in comparative example 1 and SAPO-17-seed-1 as prepared in example 1 at a test temperature of 77K and a test pressure of 0-1bar, respectively, for N 2 Adsorption/desorption curves.
Detailed Description
The invention provides a preparation method of an SAPO-17 molecular sieve, which comprises the following steps:
mixing phosphoric acid, an aluminum source, a silicon source, a template agent and water, and aging to obtain an aged product;
mixing the aged product with SAPO-17-180 molecular sieve crystal seeds, and gelatinizing to obtain gel;
crystallizing the gel under the microwave condition to obtain a crystallized product;
and calcining the crystallized product to obtain the SAPO-17 molecular sieve.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
According to the invention, phosphoric acid, an aluminum source, a silicon source, a template agent and water are mixed and aged to obtain an aged product. In the invention, the silicon source is preferably one or more of Ludox-AS, tetraethoxysilane and silica sol; the silica content in the silica sol is preferably 30 to 40wt%, more preferably 40wt%. When the silicon source is preferably selected from the above silicon sources, the ratio of different types of silicon sources is not particularly limited, and any ratio may be used.
In the invention, the aluminum source is preferably one or more of pseudo-boehmite, aluminum isopropoxide and aluminum nitrate; when the aluminum source is preferably selected from the above-mentioned aluminum sources, the ratio of the aluminum sources in different types is not particularly limited in the present invention, and any ratio may be used.
In the present invention, the templating agent is preferably cyclohexylamine, quinuclidine, N' -tetramethyl-1,6-hexanediamine.
In the present invention, the amounts of the silicon source, the aluminum source and the phosphoric acid are respectively SiO 2 、Al 2 O 3 And P 2 O 5 The molar ratio of the template, the silicon source, the aluminum source, the phosphoric acid and the water is preferably (0.8-3): (0.1-0.4): (0.4-2.0): (0.8-1.0): (30 to 60), more preferably (1.5 to 2.5): (0.15-0.2): (0.5-1.2): (0.9-1.0): (35-50), most preferably (1.8-2.0): (0.15 to 0.8): (0.8-1.0): 1.0: (35-45).
In the present invention, the process of mixing phosphoric acid, aluminum source, silicon source, templating agent and water preferably comprises the steps of:
carrying out first mixing on water and phosphoric acid to obtain a first mixed system;
carrying out second mixing on the first mixed system and an aluminum source to obtain a second mixed system;
and performing third mixing on the second mixed system, the silicon source and the template agent.
The time for the first mixing is not specially limited, and the raw materials can be uniformly mixed. In the present invention, the time of the second mixing is preferably 1 to 1.5 hours; the time for the third mixing is preferably 10 to 60min; in the present invention, the first mixing, the second mixing and the third mixing are preferably stirring mixing, and the stirring mixing speed in the present invention is not particularly limited, and may be a stirring speed well known in the art. In the present invention, the first mixing, the second mixing and the third mixing are preferably performed at room temperature.
In the present invention, the aging is preferably carried out under oil bath + stirring conditions, and the temperature of the aging is preferably 60 to 100 ℃, more preferably 80 to 90 ℃, and the time is preferably 10 to 30 hours, more preferably 20 to 24 hours. The stirring speed is not specially limited, and the smooth aging is ensured. The invention can make the reaction system more uniformly mixed by aging under the heating condition, is beneficial to complete crystallization and improves the crystallization degree of crystallization. In the aging process, the mixed reactants of phosphoric acid, an aluminum source, a silicon source, a template agent and water are changed into a transparent colloid state, so that the formation of crystal nuclei is promoted, the induction period is shortened, and the formation of the crystal nuclei is accelerated.
After an aging product is obtained, the aging product is mixed with SAPO-17-180 molecular sieve crystal seeds for gelation to obtain gel. In the invention, the preparation method of the SAPO-17-180 molecular sieve seed crystal preferably comprises the steps of mixing phosphoric acid, an aluminum source, a silicon source, a template agent and water, carrying out first aging, carrying out microwave crystallization on an obtained product under the microwave condition, and calcining the obtained product to obtain the SAPO-17 molecular sieve seed crystal.
In the present invention, the first aging time is preferably 20 to 30 hours, more preferably 24 hours, and the temperature is preferably 80 to 100 ℃. In the invention, the equipment adopted for microwave crystallization is preferably a Milestone ETHOS-D microwave heater, the power is preferably 280-300W, and the temperature rise program is preferably carried out for raising the temperature to 160-250 ℃ within 3-10 min; the temperature of the microwave crystallization is preferably 160-250 ℃, more preferably 190-210 ℃, and further preferably 200 ℃; the time is preferably 2.5 to 3.5 hours, more preferably 3 hours. In the invention, the average grain size of the SAPO-17-180 molecular sieve seed crystal is 8-14 μm, preferably 10-12 μm; the crystal morphology structure is a hexagonal prism structure.
The invention utilizes the crystal seeds to crystallize the gel, can further reduce the crystallization time, and can obtain the SAPO-17 molecular sieve with complete crystallization within 1 minute.
In the invention, the time for mixing the aged product with the SAPO-17-180 molecular sieve crystal seed is preferably 10-20 min; the mixing method is preferably stirring mixing, and the stirring speed in the present invention is not particularly limited, and may be any stirring speed known in the art.
In the present invention, the amounts of the silicon source, the aluminum source and the phosphoric acid are respectively SiO 2 、Al 2 O 3 And P 2 O 5 The mass ratio of the mass of the SAPO-17-180 molecular sieve seed crystal to the total mass of the silicon source, the aluminum source and the phosphoric acid is preferably (0.05-0.1): 1, and more preferably 0.1: (1).
In the present invention, the temperature of the gelation is preferably 80 to 100 ℃, more preferably 85 to 90 ℃; the time for the gelation is preferably 5 to 60min, more preferably 10 to 20min; the gelation is preferably carried out under stirring conditions, and the stirring rate is not particularly limited in the present invention, so that the gelation can be smoothly carried out. During the gelation process, the mixture of phosphoric acid, aluminum source, silicon source, template agent, water and seed crystal is transformed into a gel state, and the seed crystal is dissolved during the process to gradually form a crystal nucleus.
After the gel is obtained, the invention crystallizes the gel under the microwave condition to obtain a crystallized product.
In the invention, the microwave condition is preferably provided by a microwave reactor, the temperature rise program of the microwave reactor is preferably to rise to 160-250 ℃ within 3-10 min, and the power is preferably 280-300W. In an embodiment of the invention, the microwave reactor is in particular a milestone ethos-D microwave heater.
In the present invention, the crystallization temperature is preferably 160 to 250 ℃, more preferably 190 to 210 ℃, further preferably 200 ℃, and the time is preferably 1 to 180min, more preferably 10 to 120min, further preferably 30 to 60min. In the invention, the crystallization mode is preferably static crystallization, and the equipment adopted by the static crystallization is not particularly limited, and the static crystallization equipment well known in the art can be adopted; in the examples of the present invention, the static crystallization was performed in a reaction vessel.
In the crystallization process, part of formed crystal nuclei in the gel gradually grow into molecular sieve crystals with regular shapes, and the process comprises the processes of continuing forming the crystal nuclei and growing the crystal nuclei into crystals.
After the crystallization is finished, the invention preferably carries out solid-liquid separation on the system obtained after the crystallization, washes the obtained product until the pH value is 7, and dries to obtain the crystallized product. The solid-liquid separation mode in the present invention is not particularly limited, and a solid-liquid separation mode well known in the art may be adopted, specifically, suction filtration or centrifugal separation, and preferably, centrifugal separation is adopted. The process of the water washing is not particularly limited, and the washing can be carried out according to the process well known in the field; the purpose of the water washing is to remove impurities remaining on the surface of the sample. In the present invention, the drying temperature is preferably 60 to 80 ℃; the drying time is preferably 10 to 12 hours. The method for drying is not particularly limited in the present invention, and the drying can be performed by a method well known in the art; in the embodiment of the present invention, the drying manner is drying.
In the invention, the crystallization product is SAPO-17-molecular sieve containing template agent, the average grain size of the crystallization product is preferably 0.2-0.6 μm, more preferably 0.2-0.4 μm, and the morphology is hexagonal prism structure.
After obtaining the crystallized product, the invention calcines the crystallized product to obtain the SAPO-17 molecular sieve. In the present invention, the temperature of the calcination is preferably 550 to 700 ℃, more preferably 600 to 650 ℃; the time is preferably 4 to 8 hours, more preferably 6 hours. The temperature rise rate of the temperature rising to the calcining temperature is not specially limited and can be adjusted according to actual requirements; in the embodiment of the present invention, the temperature increase rate is 1 deg.C/min. In the present invention, the atmosphere for the calcination is preferably an air atmosphere. The template agent is removed by calcination.
The invention provides the SAPO-17 molecular sieve prepared by the preparation method of the technical scheme. In the invention, the SAPO-17 molecular sieve has good crystallinity and regular appearance; the shape of the SAPO-17 molecular sieve is hexagonal prism, and the side length of the hexagonal prism is 0.66 mu m multiplied by 0.26 mu m. .
The invention provides the technical scheme that the SAPO-17 molecular sieve is used as CO 2 The application of the adsorbent. In the present invention, the SAPO-17 molecular sieve is taken as CO 2 Before the adsorbent is used, the SAPO-17 molecular sieve is preferably subjected to activation, and the activation preferably comprises the following steps: activating the SAPO-17 molecular sieve for 4-10 h at 200-350 ℃ under a vacuum condition; the degree of vacuum in the present invention is not particularly limited, and a degree of vacuum known in the art may be used. The invention removes the moisture, impurities and pollutants on the surface of the molecular sieve by activation.
In the invention, SAPO-17 molecular sieve adsorbs CO 2 The mechanism of (1) is as follows: due to CO 2 Kinetic diameter of less than N (0.33 nm) 2 Kinetic diameter (0.364 nm), charge-balancing protons in SAPO-17 molecular sieve, with CO 2 There is a strong interaction that allows CO to react 2 Preferentially enter and occupy the tunnel, or so 2 Difficult access to thereby realize CO 2 And N 2 The high-efficiency separation is realized.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following example 1, the preparation process of the used SAPO-17-180 molecular sieve seed crystal is specifically as follows: adding 6.92g of phosphoric acid and 18.40g of water into a 100mL round-bottom flask, fixing the round-bottom flask on a magnetic stirrer by using an iron support, stirring at room temperature for 10min, adding 4.08g of pseudo-boehmite into a stirring system, and continuing to stir at room temperature for 1h; after stirring uniformly, adding 0.72g of Ludox AS-40 and 10.42g of N, N' -tetramethyl-1,6-hexanediamine into the flask, and continuing stirring at room temperature for 10min; fixing the flask in an oil bath, setting the temperature to be 80 ℃, and stirring and aging for 24 hours;
after the aging is finished, transferring the mixture into a microwave reaction tank while the mixture is hot, using a Milestone ETHOS-D microwave heater with the power of 300W, raising the temperature to 200 ℃ in a temperature raising program of 5min, and maintaining the temperature at 200 ℃ for 180min for crystallization; and after crystallization is finished, taking out a solid-liquid mixture in the microwave reaction tank, repeatedly cleaning a solid sample with water until the pH of the sample is =7, drying the recovered solid sample in a 60 ℃ oven for 12h, putting the dried solid sample into a muffle furnace, setting a temperature raising program of raising the temperature to 550 ℃ at a rate of 1 ℃/min, keeping the temperature at 550 ℃ and calcining for 6h to obtain SAPO-17 seed crystals, and marking as SAPO-17-180.
Example 1
Adding 6.92g of phosphoric acid and 18.40g of water into a 100mL round-bottom flask, fixing the round-bottom flask on a magnetic stirrer by using an iron support, stirring at room temperature for 10min, adding 4.08g of pseudo-boehmite into a stirring system, and continuing to stir at room temperature for 1h; after stirring uniformly, adding 0.72g of Ludox AS-40 and 10.42g of N, N' -tetramethyl-1,6-hexanediamine into the flask, and continuing stirring at room temperature for 10min; fixing the flask in an oil bath, setting the temperature to be 80 ℃, and stirring and aging for 24 hours;
after the aging is finished, adding 1.172g of seed crystal (SAPO-17-180) into the obtained system, continuing stirring for 10min at 80 ℃, transferring the obtained gel into a microwave reaction tank, using a Milestone ETHOS-D microwave heater with the power of 300W, raising the temperature to 200 ℃ by a temperature raising program of 5min, maintaining x min (x =1, 3, 5, 10, 15, 30, 60, 120 and 180) at 200 ℃, and crystallizing;
after crystallization is completed, taking out a solid-liquid mixture in a microwave reaction tank, repeatedly washing a solid sample with water until the pH of the sample is =7, drying the recovered solid sample in a 60 ℃ drying oven for 12 hours, putting the dried solid sample into a muffle furnace, setting a temperature rise program of 1 ℃/min to 550 ℃, keeping the temperature at 550 ℃ and calcining for 6 hours to obtain the SAPO-17 molecular sieve; a sample prepared with a crystallization time of 1min is named as SAPO-17-seed-1.
Comparative example 1
Adding 6.92g of phosphoric acid and 18.40g of water into a 100mL round-bottom flask, fixing the round-bottom flask on a magnetic stirrer by using an iron support, stirring at room temperature for 10min, adding 4.08g of pseudo-boehmite into a stirring system, and continuing to stir at room temperature for 1h; after stirring uniformly, adding 0.72g of Ludox AS-40 and 10.42g of N, N' -tetramethyl-1,6-hexanediamine into the flask, and continuing stirring at room temperature for 10min; fixing the flask in an oil bath, setting the temperature to be 80 ℃, and stirring and aging for 24 hours;
after the aging is finished, transferring the mixture into a microwave reaction tank while the mixture is hot, using a Milestone ETHOS-D microwave heater, heating to 200 ℃ for 5min by using a power of 300W, and maintaining ymin (y =0, 5, 15, 30, 60, 120 and 180) at 200 ℃ for crystallization; after crystallization is finished, taking out a solid-liquid mixture in a microwave reaction tank, repeatedly cleaning a solid sample with water until the pH =7 of the sample, drying the recovered solid sample in a 60 ℃ oven for 12h, putting the dried solid sample into a muffle furnace, setting a temperature rise program of 1 ℃/min to 550 ℃, keeping the temperature at 550 ℃ and calcining for 6h to obtain SAPO-17 seed crystals, and naming the sample obtained with crystallization time of 180min as SAPO-17-180 (the Si/(Si + Al + P) molar ratio of SAPO-17-180 is 0.037); the sample obtained after the crystallization time is 30min is named as SAPO-17-30 (the Si/(Si + Al + P) molar ratio of SAPO-17-30 is 0.038); the average grain size of the prepared SAPO-17-180 seed crystal is 8-14 mu m.
Comparative example 2
Adding 6.92g of phosphoric acid and 18.40g of water into a 100mL round-bottom flask, fixing the round-bottom flask on a magnetic stirrer by using an iron support, stirring at room temperature for 10min, adding 4.08g of pseudo-boehmite into a stirring system, and continuing to stir at room temperature for 1h; after stirring uniformly, adding 0.72g of Ludox AS-40 and 10.42g of N, N' -tetramethyl-1,6-hexanediamine into the flask, and continuing stirring at room temperature for 10min; and (3) fixing the flask in an oil bath, setting the temperature to be 80 ℃, and stirring and aging for 24 hours to obtain a molecular sieve sample.
Comparative example 3
Adding 6.92g of phosphoric acid and 18.40g of water into a 100mL round-bottom flask, fixing the round-bottom flask on a magnetic stirrer by using an iron support, stirring at room temperature for 10min, adding 4.08g of pseudo-boehmite into a stirring system, and continuing to stir at room temperature for 1h; after stirring uniformly, adding 0.72g of Ludox AS-40 and 10.42g of N, N' -tetramethyl-1,6-hexanediamine into the flask, and continuing stirring at room temperature for 10min; fixing the flask in an oil bath, setting the temperature to be 80 ℃, and stirring and aging for 24 hours; and after the aging is finished, adding 10wt% of seed crystal (SAPO-17-180) into the obtained system, and continuously stirring for 10min to obtain a molecular sieve sample.
Characterization of
1) XRD characterization is carried out on the SAPO-17 molecular sieve prepared in example 1 under different crystallization time conditions, and the result is shown in figure 1. As can be seen from figure 1, the product synthesized under different crystallization time conditions is the SAPO-17 molecular sieve, shows a structure, has no other impurity phase, and can obtain the pure-phase SAPO-17-seed-1 molecular sieve within 1 min.
2) SEM representation is carried out on the SAPO-17 molecular sieve prepared in example 1, and the results are shown in figure 2, wherein scales are 1 μm; wherein, (a-i) are respectively SAPO-17 molecular sieve SEM images of 1, 3, 5, 10, 15, 30, 60, 120 and 180min crystallization time; as can be seen from FIG. 2, the synthesized SAPO-17-seed-1 has a small crystal grain size of 0.66 μm by 0.26. Mu.m.
3) XRD characterization is carried out on the seed crystal samples prepared in different crystallization time according to the comparative example 1, the result is shown in figure 3, and as can be seen from figure 3, the synthesized product is the SAPO-17 zeolite molecular sieve, the overlap ratio of the XRD pattern of the synthesized product and the standard SAPO-17 molecular sieve is good, and the SAPO-17-180 crystallinity is good.
4) SEM characterization of the seed crystals SAPO-17-180 and SAPO-17-30 prepared in comparative example 1, the results are shown in FIG. 4, wherein (a) and (b) are SEM images of SAPO-17-180; (c) And (d) is an SEM image of SAPO-17-30 on a 10 μm scale for (a) and (c) and on a 1 μm scale for (b) and (d); as can be seen from FIG. 4, the crystal form of the seed crystal SAPO-17-180 is complete, the morphology is a regular hexagonal prism structure, and the seed crystal is a pure phase.
4) XRD characterization of the sample prepared in comparative example 2 gave the results shown in FIG. 3; the sample at 0min in FIG. 3 is a sample that is not crystallized in the microwave reactor, and as can be seen from FIG. 3, this sample is in an amorphous phase.
5) XRD characterization of the sample prepared in comparative example 3 gave the results shown in FIG. 1; the 0min sample in FIG. 1 is a sample that is not crystallized in the microwave reactor, and as can be seen from FIG. 1, this sample is in an amorphous phase.
Application example
Carrying out gas selective adsorption separation tests by using the SAPO-17-seed-1 zeolite molecular sieve prepared in example 1 and the SAPO-17-30 prepared in comparative example 1 as adsorbents, activating a SAPO-17 zeolite molecular sieve sample at 350 ℃ for 10h under a vacuum condition before the tests, cooling the sample to room temperature, and carrying out single-component gas isothermal adsorption and desorption tests, namely N 2 And CO 2 The test temperature is 273K,298K, the test pressure is 0-1bar, CO 2 And N 2 The adsorption amount and the adsorption separation ratio of (2) are shown in fig. 5.
As can be seen from FIG. 5, the SAP O-17-seed-1 molecular sieve and CO are synthesized ultrafast within 1min under the synergistic microwave-assisted hydrothermal system of the seed crystal 2 Has stronger interaction force, thereby being in CO 2 /N 2 The adsorption separation of (2) shows higher separation performance. In FIG. 5, (a) and (b) are CO for SAPO-17-30 and SAPO-17-seed-1 at 273K and 298K, respectively 2 And N 2 An adsorption-desorption curve; (c-1) and (c-2) are SAPO-17-seed-1 and SAPO-17-30 molecular sieve pairs CO respectively 2 /N 2 The adsorption separation curves under 273K and 298K are obtained by using the common method for predicting the adsorption of the binary mixed gas by using the single-component gas adsorption isotherm obtained by experiments, namely, an IAST model is utilized, and fitting calculation is carried out by using a double-point Langmuir-Freundlich formula, so that SAPO-17-seed-1 on CO under 100KPa, 273K and 298K 2 /N 2 The separation ratios (118.37 and 117.04) are both higher than SAPO-17-30 (30.709 and 34.299);
FIG. 5 (d) shows the heat of adsorption (Q) for SAPO-17-30 and SAPO-17-seed-1 molecular sieves st ) Curves are obtained by using the visual formula for CO at 273K and 298K 2 The adsorption isotherm is calculated by fitting, and it can be seen from (d) in FIG. 5 that the adsorption heat of SAPO-17-seed-1 is increased by 38% compared with SAPO-17-30, which indicates that SAPO-17-seed-1 is compared with SAPO-17-30, and compared with SAPO-17-30, the adsorption heat is increased by 38% compared with SAPO-17-1 2 Has stronger interaction.
FIG. 6 shows SAPO-17-30 and SAPO-17-180 as prepared in comparative example 1 and SAPO-17-seed-1 as prepared in example 1 at a test temperature of 77K and a test pressure of 0-1bar, respectively, for N 2 Adsorption/desorption profile. As can be seen from FIG. 6, SAPO-17-30, SAPO-17-seed-1, and SAPO-17-180 are all microporous structures. According to the N at 77K of SAPO-17-seed-1 and SAPO-17-30 in FIG. 6 2 The adsorption test is carried out, and the calculated specific surface area of the SAPO-17-seed-1 molecular sieve is 594m 2 Per g, total pore volume 0.29cm 3 The specific surface area and the pore volume are respectively increased by 16 percent and 21 percent compared with SAPO-17-30.
The specific surface area of the SAPO-17-30 is 511m 2 (ii)/g, total pore volume 0.24cm 3 The specific surface area of SAPO-17-180 is 524m 2 (ii)/g, total pore volume 0.25cm 3 /g。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. The preparation method of the SAPO-17 molecular sieve is characterized by comprising the following steps of:
mixing phosphoric acid, an aluminum source, a silicon source, a template agent and water, and aging to obtain an aged product;
mixing the aged product with SAPO-17-180 molecular sieve crystal seeds, and gelatinizing to obtain gel;
crystallizing the gel under the microwave condition to obtain a crystallized product;
calcining the crystallized product to obtain the SAPO-17 molecular sieve;
the silicon source, the aluminum source and the phosphoric acid are respectively SiO 2 、Al 2 O 3 And P 2 O 5 The mass ratio of the mass of the SAPO-17-180 molecular sieve seed crystal to the total mass of the silicon source, the aluminum source and the phosphoric acid is (0.05-0.1): 1;
the microwave condition is provided by a microwave reactor, and the temperature rise program of the microwave reactor is to raise the temperature to 160-250 ℃ within 3-10 min, and the power is 280-300W.
2. The preparation method according to claim 1, wherein the silicon source is one or more of Ludox-AS, ethyl orthosilicate and silica sol; the aluminum source is one or more of pseudo-boehmite, aluminum isopropoxide and aluminum nitrate; the template agent is cyclohexylamine, quinuclidine or N, N, N ', N' -tetramethyl-1,6-hexanediamine.
3. The method according to claim 1 or 2, wherein the amounts of the silicon source, the aluminum source and the phosphoric acid are SiO, respectively 2 、Al 2 O 3 And P 2 O 5 The molar ratio of the template agent, the silicon source, the aluminum source, the phosphoric acid and the water is (0.8-3): (0.1-0.4): (0.4-2.0): (0.8-1.0): (30-60).
4. The process according to claim 1, wherein the aging is carried out at a temperature of 60 to 100 ℃ for a period of 10 to 30 hours.
5. The method according to claim 1, wherein the crystallization temperature is 160-250 ℃ and the crystallization time is 1-180 min.
6. The preparation method according to claim 1, wherein the calcination is carried out at a temperature of 550 to 700 ℃ for 4 to 8 hours.
7. The SAPO-17 molecular sieve prepared by the preparation method of any one of claims 1 to 6, wherein the morphology of the SAPO-17 molecular sieve is hexagonal prism shaped, and the side length of the hexagonal prism shaped is 0.66 μm x 0.26 μm.
8. SAPO-17 of the molecular sieve of claim 7 as CO 2 The application of the adsorbent.
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