CN115057452A - Method for rapidly preparing molecular sieve and molecular sieve membrane by using 'clean' crystal seeds - Google Patents
Method for rapidly preparing molecular sieve and molecular sieve membrane by using 'clean' crystal seeds Download PDFInfo
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Abstract
The invention provides a method for rapidly preparing a molecular sieve and a molecular sieve membrane by using 'clean' seed crystals, which particularly relates to a method for rapidly synthesizing the molecular sieve or the molecular sieve membrane by separately heating the seed crystals or a seed crystal base membrane and a synthetic solution and mixing at a high temperature instead of room temperature. The seed crystal is independently heated, so that the problems of dissolution and pollution of the seed crystal, interaction between the seed crystal and the synthetic solution and competitive growth of different molecular sieves are solved; the synthetic liquid is independently heated, the stability of the microstructure and the composition of the synthetic liquid is kept, the problem of uneven temperature field of the synthetic liquid can be effectively solved, the rapid heating of a large amount of synthetic liquid can be realized, and the problem of thermal hysteresis in the synthetic process is solved. The seed crystal and the synthetic liquid are mixed at high temperature, so that the synthetic time can be greatly shortened. In the membrane synthesis process, the synthesis time is short, so that the stable structure of the main synthesis liquid can be maintained, the synthesis liquid can be recycled, and the membrane production cost is effectively reduced.
Description
Technical Field
The invention relates to a method for rapidly preparing a molecular sieve and a molecular sieve membrane by using 'clean' seed crystals, in particular to a rapid synthesis technology for realizing the molecular sieve and the molecular sieve membrane by separately heating the seed crystals and a synthetic liquid and mixing the seed crystals and the synthetic liquid at high temperature instead of room temperature.
Technical Field
The molecular sieve has the characteristics of regular pore passages, good hydrothermal stability, good chemical stability and the like, so that the molecular sieve is widely used as a catalyst, a drying agent, an adsorbent, an ion exchange material and a membrane material; the molecular sieve membrane has the advantages of high separation efficiency, low energy consumption, environmental protection and the like, and is widely applied to liquid separation, gas separation and catalytic membrane reactors. At present, more than 250 molecular sieves have been discovered, however, only a small fraction of molecular sieves have achieved commercial use; while more than 20 molecular sieve membrane materials are developed, only the NaA molecular sieve membrane realizes the pervaporation dehydration application of the near-neutral organic solvent. The key problem restricting the wide application of the molecular sieve and the molecular sieve membrane is the cost problem, the longer synthesis time not only increases the process energy consumption, but also is not beneficial to the controllable modulation of the molecular sieve and the molecular sieve membrane microstructure, and the performances of the molecular sieve and the molecular sieve membrane in all aspects are seriously influenced. Secondly, the synthesis of a large amount of molecular sieves and molecular sieve membranes requires the use of an excessive amount of expensive organic template, so the types, application ranges and the like of the industrial molecular sieves and molecular sieve membranes are severely limited.
At present, microwave heating and oil bath heating are mainly adopted for shortening the synthesis time of the molecular sieve and the molecular sieve membrane and reducing the synthesis energy consumption. For example, in patent ZL 201810455824.6, an h0h oriented ultrathin MFI molecular sieve membrane can be synthesized within 0.5 h by adopting a microwave heating mode, and the membrane separation performance is effectively improved; the patent ZL 201510779618.7 adopts a microwave-assisted heating method to shorten the synthesis time of the MOR molecular sieve membrane to 0.1 h; in the patent ZL 200810010621.2, microwave-assisted synthesis is adopted, so that the synthesis time of the ZSM-11 molecular sieve is shortened to 1 h; the patent ZL 201810455775.6 utilizes oil bath heating to shorten the synthesis time of the SSZ-13 molecular sieve membrane to 6 hours. However, further reduction of the film synthesis time is difficult to achieve, which is mainly determined by the characteristics of the secondary growth method. Secondly, microwave and oil bath synthesis methods have difficulty in achieving rapid heating of large quantities of synthesis solution. Therefore, the development of a new molecular sieve membrane synthesis method can effectively solve the influence of thermal hysteresis problem and the like on the synthesis of the molecular sieve membrane, and has important significance for improving the utilization times of the synthesis solution while realizing the rapid synthesis of the molecular sieve membrane.
Disclosure of Invention
The invention aims to provide a method for realizing rapid synthesis of a molecular sieve and a molecular sieve membrane by using a 'clean' seed crystal method, which can not only effectively avoid the problem that a synthetic solution cannot be rapidly heated in a large scale by microwave heating and oil bath heating, realize ultra-rapid synthesis of the molecular sieve and the molecular sieve membrane, but also realize repeated utilization of a membrane-preparing synthetic solution and effectively reduce the preparation cost of the molecular sieve membrane.
The invention provides a method for rapidly preparing a molecular sieve and a molecular sieve membrane by using 'clean' crystal seeds, which comprises the steps of constructing an independent crystal seed chamber and a synthetic liquid chamber, and separately heating and synthesizing the molecular sieve and the molecular sieve membrane at high temperature. Wherein, the key step of realizing the rapid synthesis of the molecular sieve and the molecular sieve membrane in the patent is to separately heat the seed crystal, the seed crystal liquid or the seed crystal basal membrane and the synthetic liquid in the synthetic liquid chamber in the seed crystal chamber. The crystal seeds, the crystal seed liquid or the crystal seed base membrane in the crystal seed chamber are separately heated, so that the structural stability of the molecular sieve crystal seeds in the crystal seed chamber is favorably avoided, primary/secondary structural units which are easy to cause competitive growth are not generated in the heating process, the cleanness degree of the surface of the crystal seeds is ensured, and the aluminosilicate gel in the synthetic liquid can be induced to rapidly form new crystal nuclei when the crystal seeds are contacted with the synthetic liquid at high temperature, so that the molecular sieve or the molecular sieve membrane is rapidly formed; secondly, the indoor temperature, humidity and pressure of the seed crystal chamber can be adjusted by separately heating, the stability of the seed crystal and the seed crystal base film structure is ensured, and the contact between the seed crystal or the seed crystal base film and the synthetic liquid at high temperature is facilitated. The synthetic liquid is heated independently, so that the interaction between the synthetic liquid and the seed crystal in the heating process of the traditional synthetic method can be effectively avoided, and the stability of the microstructure and the composition of the synthetic liquid in the heating process can be ensured. More importantly, the method has extremely short synthesis time, and only consumes the synthesis solution near the carrier in the membrane preparation process, so that the synthesis solution can be recycled for multiple times, the production cost of the molecular sieve membrane can be effectively reduced, and particularly the synthesis cost of the molecular sieve membrane needing to use a large amount of expensive organic template agent is reduced.
The invention provides a method for rapidly preparing a molecular sieve and a molecular sieve membrane by using 'clean' crystal seeds. Wherein, the seed crystal chamber is composed of a container, a valve, a seed crystal or seed crystal liquid or a seed crystal base film; the mode of contacting and mixing the seed crystal (seed crystal basal membrane or liquid crystal) and the synthetic liquid is realized by controlling a valve and a sealing gasket which are connected with the seed crystal chamber and the synthetic liquid chamber.
The invention provides a method for rapidly preparing a molecular sieve and a molecular sieve membrane by using 'clean' seed crystals, which is characterized in that the seed crystals or seed crystal liquid in a seed crystal chamber is mainly used for rapidly synthesizing the molecular sieve; and the seed crystal basement membrane is used for the rapid synthesis of the molecular sieve membrane. Before the crystal chamber contacts with the synthetic liquid chamber, the closing and opening degree of the crystal chamber is controlled by adjusting the valve on the crystal chamber, so that the humidity, the pressure and the like in the crystal chamber are effectively controlled. Seeded based films are mainly of the 3 medium type: coating a molecular sieve seed crystal on the surface of a support by using a crystal coating technology, and drying to obtain the molecular sieve seed crystal; soaking the carrier into the synthetic solution at room temperature for 0-10 min, drying, coating molecular sieve crystal seeds on the surface of the carrier, and drying to form a seed crystal base film; thirdly, coating crystal seeds on the surface of the carrier and drying, then soaking the crystal-coated carrier into the synthetic liquid at room temperature for 0-3 h, taking out and airing to obtain the crystal-coated carrier.
The invention provides a method for rapidly preparing a molecular sieve and a molecular sieve membrane by using 'clean' seed crystals, which is characterized in that the temperature of the seed crystals, the liquid crystal or the seed crystal base membrane in a seed crystal chamber can be lower than, equal to or higher than the temperature of synthetic liquid in a synthetic liquid chamber, and the temperature range is 20-260 ℃; the temperature of the synthetic solution is within the range of 100-250 ℃, the actual temperature is determined according to the types of different molecular sieves or molecular sieve membranes, and the synthetic time is 5 s-4 h.
The invention provides a method for rapidly preparing a molecular sieve and a molecular sieve membrane by using 'clean' seed crystals, which is characterized in that two mixing modes of seed crystals, seed crystal liquid or seed crystal base membrane and synthetic liquid in a seed crystal chamber are provided, firstly, the seed crystals, the seed crystal liquid or the seed crystal base membrane are injected into the synthetic liquid; secondly, injecting the high-temperature synthetic liquid into a seed crystal chamber to mix the high-temperature synthetic liquid with seed crystals, liquid crystal or seed crystal base films. The mixing of the seed crystal (seed crystal liquid or seed crystal base film) and the synthetic liquid is realized by gravity, pressure or mechanical conveying and the like; the mixing mode is mainly determined according to the temperature of the synthesis liquid chamber, the temperature of the seed crystal chamber and the synthesis conditions, and usually, the seed crystal liquid or the seed crystal base membrane is added into the high-temperature synthesis liquid; if the temperature is required to be changed for synthesis, the synthetic fluid is added into a low-temperature or high-temperature seed crystal chamber and the temperature of the seed crystal chamber is kept unchanged.
The method for rapidly preparing the molecular sieve and the molecular sieve membrane by using the clean crystal seeds is characterized in that the method can be used for synthesizing different types of molecular sieves and molecular sieve membranes (such as MFI, SAPO-34, SSZ-13, DDR, CHA and the like, but not limited to the listed molecular sieves and molecular sieve membranes) and can also be used for synthesizing partial Metal Organic Framework (MOF) materials; meanwhile, the method can be used for the rapid preparation of the anticorrosive coating.
The method for rapidly preparing the molecular sieve and the molecular sieve membrane by using the clean seed crystal is characterized in that in the membrane preparation process, the synthetic liquid can be repeatedly used for synthesizing the molecular sieve membrane, so that the application cost of the molecular sieve membrane can be effectively reduced. Meanwhile, the method can be used for multistage synthesis and continuous production of the molecular sieve membrane. The molecular sieve and the molecular sieve membrane prepared by the clean seed crystal method are mainly used for catalysis, adsorption, liquid separation, gas separation, membrane reactor and the like.
Drawings
FIG. 1 is a schematic diagram of the rapid synthesis of molecular sieves and molecular sieve membranes using a "clean" seed crystal process.
FIG. 2 is a mechanism diagram of rapid synthesis of molecular sieve and molecular sieve membrane by "clean" seed crystal method.
FIG. 3 is an electron microscope photograph of MFI, SAPO-34, SSZ-13 and DDR molecular sieves prepared rapidly by using a 'clean' seed crystal method.
FIG. 4 XRD patterns of MFI, SAPO-34, SSZ-13 and DDR molecular sieves.
FIG. 5 is a Nuclear Magnetic Resonance (NMR) chart (a) and a gas adsorption curve (b) of an MFI molecular sieve.
FIG. 6 shows the electron micrographs of MFI, SAPO-34 and SSZ-13 molecular sieve membranes.
FIG. 7 XRD patterns of SAPO-34 and SSZ-13 molecular sieve membranes.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to better illustrate the method for rapidly preparing the molecular sieve and the molecular sieve membrane provided by the invention, various synthesized molecular sieves and molecular sieve membranes are used for gas adsorption characterization, organic solvent dehydration, organic matter separation and gas separation, specific examples are given, but the protection scope of the patent is not limited to the examples.
Example 1
0.005 g of MFI molecular sieve was added to the seed chamber, and the seed chamber valve was held closed (as shown in FIG. 1). Tetraethoxysilane, tetrapropylammonium hydroxide and deionized water are used for preparing 30 mL of synthetic solution, and the molar ratio of the synthetic solution is as follows: SiO 2 2 : EtOH: TPAOH: H 2 And O =1: 4.0: 0.25: 10, pouring the prepared synthetic liquid into a synthetic liquid chamber (a stainless steel synthesis kettle), heating the crystallization chamber and the synthetic liquid chamber to 210 ℃, after the temperature of the synthetic liquid is stable, using a pump body to press the synthetic liquid in the synthetic liquid chamber into the crystallization chamber, synthesizing for 5 s, and obtaining the MFI molecular sieve sample after centrifugal washing and drying. The microstructure, XRD spectrogram, NMR chart and gas adsorption curve of the prepared MFI molecular sieve are respectively shown in figures 3-5. The mechanism of rapid growth of molecular sieves is shown in figure 2. Research results show that the prepared MFI molecular sieve has the average grain diameter of 100 nm, good crystallinity and no silicon hydroxyl defect.
Example 2
0.01 g of MFI molecular sieve with the particle size of 1 mu m is added into 1 mL of deionized water, ultrasonic treatment is carried out for one hour, 0.5 mL of seed crystal liquid is added into a seed crystal chamber, and the valve of the seed crystal chamber is kept closed. Tetraethoxysilane, tetrapropylammonium hydroxide and deionized water are used for preparing 40 mL of synthetic solution, and the molar ratio of the synthetic solution is as follows: SiO 2 2 : EtOH: TPAOH: H 2 O =1: 4.0: 0.25: 10, and the prepared synthesis solution was poured into the synthesis solution chamber. And (3) respectively heating the crystallization chamber and the synthesis liquid chamber to 200 ℃ and 220 ℃ by utilizing two ovens, pressing the crystal seeds in the crystallization chamber into the synthesis liquid chamber by using an injector after the temperature of the synthesis liquid is stable, shaking the synthesis chamber to uniformly mix the crystal seeds, synthesizing for 60 s, and centrifugally washing and drying to obtain the MFI molecular sieve sample. Research shows that the MFI molecular sieve prepared by the method is almost completely consistent with the molecular sieve in the example 1 in structure and the like.
Example 3
0.01 g of SAPO-34 molecular sieve with the particle size of 0.6 mu m is added into 1 mL of deionized water, ultrasonic treatment is carried out for one hour, 0.5 mL of seed crystal liquid is added into a seed crystal chamber, and the valve of the seed crystal chamber is kept closed. Silica sol, tetraethyl ammonium hydroxide, phosphoric acid, aluminum isopropoxide and deionized water are used for preparing 25 mL of synthetic solution, and the molar ratio of the synthetic solution is as follows: al (Al) 2 O 3 : P 2 O 5 : SiO 2 : TEAOH: H 2 O =1: 1.2: 0.6: 2.0: 40, and the prepared synthesis solution was poured into the synthesis solution chamber. And (2) respectively heating the temperature of the crystallization chamber and the temperature of the synthesis liquid chamber to 240 ℃ and 200 ℃ by using two ovens, pressing the crystal seeds in the crystallization chamber into the synthesis liquid chamber by using high-pressure gas after the temperature of the synthesis liquid is stable, shaking the synthesis chamber to uniformly mix the crystal seeds, synthesizing for 60 s, and obtaining the SAPO-34 molecular sieve sample after centrifugal washing and drying. The microstructure and XRD spectrogram of the prepared SAPO-34 molecular sieve are shown in figures 3 and 4.
Example 4
0.01 g of SAPO-34 molecular sieve with the particle size of 0.6 μm is added into the seed crystal chamber, and the valve of the seed crystal chamber is kept open. Silica sol, tetraethylammonium hydroxide, phosphoric acid, aluminum isopropoxide, dipropylamine and deionized water are used for preparing 25 mL of synthetic solution, and the molar ratio of the synthetic solution is as follows: al (Al) 2 O 3 : 1.0 P 2 O 5 : 0.5 SiO 2 : 1.0 TEAOH: 1.6 DPA: 150 H 2 O =1: 1: 0.5: 1.0: 1.6: 150, and the prepared synthesis solution was poured into the synthesis solution chamber. And (2) respectively heating the crystal seed chamber and the synthesis liquid chamber to 260 ℃ and 220 ℃ by utilizing two ovens, blowing the crystal seeds in the crystal seed chamber into the synthesis liquid chamber by using high-pressure gas after the temperature of the synthesis liquid is stable, shaking the synthesis chamber to uniformly mix the crystal seeds, synthesizing for 2 min, and obtaining the SAPO-34 molecular sieve sample after centrifugal washing and drying. The prepared SAPO-34 molecular sieve has the similar micro-morphology and the like as in example 3.
Example 5
0.02 g of SSZ-13 molecular sieve having a particle size of 3.0 μm was added to the seed cell, and the seed cell valve was kept open. Silica sol, N, N, N-trimethyl-1-adamantyl ammonium hydroxide, aluminum hydroxide, sodium hydroxide and deionized water are used for preparing 25 mL of synthetic solution, and the molar ratio of the synthetic solution is as follows: SiO 2 2 : Al 2 O 3 : Na 2 O: TMAdaOH: H 2 O =1: 0.01: 0.1: 0.6: 44, and the prepared synthesis solution was poured into the synthesis solution chamber. Keeping the temperature of the crystal seed chamber at room temperature (about 20 ℃), heating the synthesis chamber to 250 ℃, blowing the crystal seeds in the crystal seed chamber into the synthesis liquid chamber by using high-pressure gas after the temperature of the synthesis liquid is stable, shaking the synthesis chamber to mix the crystal seeds uniformly, synthesizing for 5 min, and obtaining the SSZ-13 molecular sieve sample after centrifugal washing and drying. The microstructure and XRD spectrogram of the prepared SAPO-34 molecular sieve are shown in figures 3 and 4.
Example 6
0.01 g of DDR molecular sieve with the particle size of 1.0 μm is added into the seed crystal chamber, and the valve of the seed crystal chamber is kept closed. Preparing 25 mL of synthetic solution by using silica sol, amantadine, ethylenediamine, sodium hydroxide and deionized water, wherein the molar ratio of the synthetic solution is as follows: SiO 2 2 : H 2 ADA: EDA: NaOH =1: 100: 0.15: 1.4: 0.3, and the prepared synthesis solution was poured into the synthesis solution chamber. Heating seed crystal chamber to 100 deg.C, heating synthesis chamber to 150 deg.C, blowing seed crystal in the seed crystal chamber into the synthesis chamber with high-pressure gas after the temperature of the synthesis solution is stable, shaking the synthesis chamber to mix well, synthesizing for 4 hr, centrifuging, washing and drying to obtain the final productDDR molecular sieve samples. The micro-morphology and XRD spectrogram of the prepared DDR molecular sieve are shown in figures 3 and 4.
Example 7
Preparing 2 wt.% SAPO-34 seed crystal liquid by using deionized water, coating seed crystals on the surface of a hollow fiber support body by adopting a dip coating method, drying for 3 hours at 65 ℃, putting the hollow fiber support body into a seed crystal chamber, and keeping a valve of the seed crystal chamber open. Using silica sol, tetraethyl ammonium hydroxide, phosphoric acid, aluminum isopropoxide, dipropylamine and deionized water to prepare 45 mL of synthetic liquid, wherein the molar ratio of the synthetic liquid is as follows: al (Al) 2 O 3 : 1.0 P 2 O 5 : SiO 2 : TEAOH: DPA: H 2 O =1: 1: 0.5: 1.0: 1.6: 150, and the prepared synthesis solution was poured into the synthesis solution chamber. And heating the temperature of the crystal chamber and the synthesis liquid chamber to 220 ℃ by using an oven, closing a valve of the crystal chamber after the temperature of the synthesis liquid is stable, allowing the synthesis liquid to flow into the crystal chamber under the action of gravity, standing for synthesis for 1-120 min, cleaning and drying after synthesis to obtain the SAPO-34 molecular sieve membrane, wherein the growth mechanism of the membrane layer is shown in figure 2. The micro-membrane appearance and XRD of the SAPO-34 molecular sieve prepared in 1 min of synthesis are shown in figures 6 and 7. Preparation of SAPO-34 molecular sieve membranes for H at room temperature at different times 2 /N 2 、CO 2 /CH 4 The separation results are shown in table 1.
Example 8
Preparing 100 mL of synthetic solution by using silica sol, N, N, N-trimethyl-1-adamantyl ammonium hydroxide, aluminum hydroxide, sodium hydroxide and deionized water, wherein the molar ratio of the synthetic solution is as follows: SiO 2 2 : Al 2 O 3 : Na 2 O: TMAdaOH: H 2 O =1: 0.01: 0.1: 0.6: 55, and 50 mL of the synthesis solution was poured into the synthesis solution chamber. Preparing 1 wt.% of SSZ-13 liquid crystal by using deionized water, coating seed crystals on the surface of a hollow fiber support body by adopting a vacuum suction method, drying for 2 h at 60 ℃, then immersing the hollow fiber support body into the residual synthetic liquid for 3 h, taking out and drying the hollow fiber support body, then placing the hollow fiber support body into a crystal room, and keeping the valve of the crystal room closed. The temperature of the crystallization chamber and the temperature of the synthesis liquid chamber are respectively heatedAnd (3) when the temperature of the synthesis liquid is 200 ℃ and 220 ℃, pumping the synthesis liquid into a crystal room by using a pump after the temperature of the synthesis liquid is stable, standing and synthesizing for 30 min, and cleaning and drying after synthesis to obtain the SSZ-13 molecular sieve membrane. The microstructure and XRD of the prepared SSZ-13 molecular sieve membrane are shown in figures 6 and 7. The prepared SSZ-13 molecular sieve membrane is used for H at room temperature 2 /N 2 、CO 2 /CH 4 Upon separation, H 2 And CO 2 Permeability of 6X 10 respectively -7 molm -2 s -1 Pa -1 And 1.2X 10 -6 molm -2 s -1 Pa -1 ，H 2 /N 2 Selectivity is 11, CO 2 /CH 4 The selectivity was 125.
Example 9
Preparing 100 mL of synthetic solution by using silica sol, sodium metaaluminate, potassium hydroxide and deionized water, wherein the molar ratio of the synthetic solution is as follows: SiO 2 2 : Al 2 O 3 : Na 2 O: K 2 O: H 2 O = 22: 1: 1: 14.5: 4400, 50 mL of the synthesis solution was poured into the synthesis solution chamber. And (3) immersing the tubular carrier into the residual synthetic liquid for 10 min, taking out and drying, coating CHA crystal seeds on the surface of the tubular carrier by using a wiping method, drying for 10 min at the temperature of 60 ℃, then placing the tubular carrier into a crystal chamber, and keeping the valve of the crystal chamber closed. And (3) heating the crystal room chamber and the synthesis liquid chamber to 140 ℃ and 160 ℃ respectively, pumping the synthesis liquid into the crystal room chamber by using a pump after the temperature of the synthesis liquid is stable, standing and synthesizing for 10 min, and cleaning and drying after synthesis to obtain the CHA molecular sieve membrane. The prepared CHA molecular sieve membrane is used for osmotic vaporization dehydration of 90 wt.% ethanol solution at 75 ℃, and the water flux is up to 18.2kgm -2 h -1 Separation factor>10000。
Example 10
Tetrapropylammonium bromide, tetraethoxysilane, sodium hydroxide and deionized water are used for preparing 100 mL of synthetic solution, and the molar ratio of the synthetic solution is as follows: NaOH TPABr SiO 2 : H 2 EtOH = 0.9: 0.9: 4: 1000: 16, 50 mL of the synthesis solution was poured into the synthesis solution chamber. Immersing the hollow fiber carrier in the synthetic liquid for 1 min, taking out, drying, coating MFI crystal seeds on the surface of the hollow fiber carrier by using a wiping method, drying for 5 min at the temperature of 60 ℃, then placing the hollow fiber carrier in a crystal chamber, and keeping the valve density of the crystal chamberAnd (5) closing. Heating the crystal chamber and the synthesis liquid chamber to 200 deg.C and 180 deg.C respectively, pumping the synthesis liquid into the crystal chamber by using a pump after the temperature of the synthesis liquid is stable, standing for synthesis for 5-20 min, cleaning and drying after synthesis to obtain MFI molecular sieve membrane with microstructure shown in FIG. 6. The MFI molecular sieve membrane prepared by synthesizing for 10 min is used for osmotic vaporization dehydration of 5 wt.% ethanol solution at 60 ℃, and the ethanol flux is up to 7.6Kgm -2 h -1 Separation factor>40; the MFI molecular sieve membrane prepared by synthesizing 20 min is used for separating dimethylbenzene (PX and OX), and the selectivity of PX/OX>10。
Example 11
Sodium silicate, sodium metaaluminate, sodium hydroxide and deionized water are used for preparing 100 mL of synthetic solution, and the molar ratio of the synthetic solution is as follows: a1 2 O 3 : SiO 2 : Na 2 O: H 2 O =1: 2: 2: 120, 50 mL of the synthesis solution was poured into the synthesis solution chamber. Coating NaA crystal seeds on the surface of the tubular carrier by using a wiping method, drying for 2 hours, then placing into the rest synthetic liquid for 1 min, taking out, drying, then placing into a crystal chamber, and keeping the valve of the crystal chamber closed. And heating the crystal chamber and the synthesis liquid chamber to 100 ℃, pumping the synthesis liquid into the crystal chamber by using a pump after the temperature of the synthesis liquid is stable, standing and synthesizing for 2 min, cleaning and drying after synthesis to obtain the NaA molecular sieve membrane. The prepared NaA molecular sieve membrane is used for osmotic vaporization dehydration of 90 wt.% ethanol solution at 75 ℃, and the water flux is up to 12.7 kgm -2 h -1 Separation factor>10000。
Example 12
Preparing 2 wt.% SAPO-34 seed crystal liquid by using deionized water, coating seed crystals on the surface of a hollow fiber support body by adopting a dip coating method, drying for 3 hours at 65 ℃, then respectively placing the hollow fiber support body into 5 seed crystal chambers, and connecting by using valves to form a multistage synthesis device; keeping the seed chamber valves closed. Preparing 100 mL of synthetic solution by using silica sol, tetraethylammonium hydroxide, phosphoric acid, aluminum isopropoxide, dipropylamine and deionized water, wherein the molar ratio of the synthetic solution is as follows: al (Al) 2 O 3 : 1.0 P 2 O 5 : SiO 2 : TEAOH: DPA: H 2 O =1: 1: 0.5: 1.0: 1.6: 150, and the prepared synthesis solution was poured into the synthesis solution chamber. Heating the temperature of each crystal chamber and the temperature of each synthesis liquid chamber to the temperature of the synthesis liquid chamber by using an ovenAnd (3) closing a crystal room valve after the temperature of the synthetic liquid is stable at 220 ℃, enabling the synthetic liquid to enter a first-stage crystal room for synthesis for 1 min, and then pressing all the synthetic liquid into a second-stage synthesis room for synthesis for 1 min. Repeating the sequence to each crystal room and synthesizing for 1 min, taking out, cleaning and drying to obtain 5 SAPO-34 molecular sieve membranes, wherein the XRD of the 5 th grade SAPO-34 molecular sieve micro-membrane is shown in figure 7. The prepared 5-branch SAPO-34 molecular sieve membrane is used for CO at room temperature 2 /CH 4 Separation of CO 2 The permeability is (3.0 +/-0.4) multiplied by 10 -6 molm -2 s -1 Pa -1 ， CO 2 /CH 4 The selectivity is 120 +/-20, which indicates that the multistage synthesis effect is good, and the synthesis solution can be reused.
Claims (9)
1. The method for rapidly preparing the molecular sieve and the molecular sieve membrane by utilizing the clean seed crystal mainly comprises the following steps:
(A) construction of seed chamber and synthetic liquid chamber
Placing a certain amount of seed crystals, seed crystal solution or seed crystal base film in a container to form a seed crystal chamber; simultaneously adding the aged molecular sieve or molecular sieve membrane synthetic fluid into another closed synthesis kettle to form a synthetic fluid chamber, wherein the crystal chamber and the synthetic fluid chamber are connected and separated with a pipeline through a valve or a sealing gasket;
(B) rapid synthesis of molecular sieve and molecular sieve membrane
And (C) heating the crystal seed chamber and the synthetic liquid chamber in the step (A) separately, opening a valve or a sealing gasket after the temperature of the synthetic liquid in the synthetic liquid chamber is stable, enabling the crystal seeds, the crystal seed liquid or the crystal seed base membrane in the crystal seed chamber to be in full contact with and mixed with the synthetic liquid in the synthetic liquid chamber, and synthesizing at a high temperature for a certain time to obtain the molecular sieve or the molecular sieve membrane.
2. The preparation method according to claim 1, characterized in that the seed crystal or seed crystal liquid in the seed crystal chamber in step (A) is mainly used for the rapid synthesis of molecular sieve; the seed crystal basement membrane is mainly used for the rapid synthesis of molecular sieve membranes.
3. The method according to claim 1, wherein the seed-crystal-based film is prepared by a method comprising the steps of (A) preparing a seed-crystal-based film in a seed-crystal chamber, which comprises mainly 3 types: coating seed crystals on the surface of a support by using crystal coating technologies such as dip coating, wiping coating, vacuum suction and the like, and drying to obtain the crystal seed crystals; soaking the carrier into the synthetic solution at room temperature for 0-10 min, drying, coating the crystal seeds on the surface of the carrier by using a crystal coating technology, and drying to obtain the crystal seeds; thirdly, coating crystals on the surface of the carrier and drying, then soaking the crystal-coated carrier into the synthetic liquid at room temperature for 0-3 hours, taking out and airing to obtain the crystal-coated carrier.
4. The method according to claim 1, wherein the temperature of the seed crystal, the seed solution or the seeded film in the seed chamber in the step (B) is lower than, equal to or higher than the temperature of the synthesis solution in the synthesis solution chamber, and the temperature is in the range of 20 to 260 ℃.
5. The production process as set forth in claim 1, wherein in the step (B), the seed chamber is kept in a closed state or an open state before communicating with the synthesis liquid chamber, and the humidity, pressure, etc. in the seed chamber are controlled by valve regulation.
6. The preparation method according to claim 1, wherein the seed crystal, the seed crystal liquid or the seed crystal base film in the seed crystal chamber in the step (B) is mixed with the synthetic liquid in two ways, namely, the seed crystal liquid or the seed crystal base film is injected into the synthetic liquid; secondly, injecting the high-temperature synthetic solution into a crystal seed chamber to mix the high-temperature synthetic solution with crystal seeds, crystal seed liquid or a crystal seed base film.
7. The preparation method of claim 1, wherein the method can be used for synthesis of different kinds of molecular sieves and molecular sieve membranes (MFI, SAPO-34, SSZ-13, DDR, CHA, etc.), and can be used for synthesis of partial Metal Organic Framework (MOF) materials.
8. The method according to claim 1, wherein the temperature of the synthesis solution in step (B) and step 7 is determined according to the type of the molecular sieve or molecular sieve membrane, and is generally in the range of 100 to 250 ℃, and the synthesis time is 5 s to 4 h.
9. The method according to claim 1, wherein the synthesis solution in step (B) is used repeatedly for the synthesis of molecular sieve membrane; the synthesis method can be used for multi-stage synthesis and continuous production of the molecular sieve membrane.
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