CN111760467A - Preparation method of T-type zeolite molecular sieve membrane - Google Patents
Preparation method of T-type zeolite molecular sieve membrane Download PDFInfo
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- CN111760467A CN111760467A CN202010731863.1A CN202010731863A CN111760467A CN 111760467 A CN111760467 A CN 111760467A CN 202010731863 A CN202010731863 A CN 202010731863A CN 111760467 A CN111760467 A CN 111760467A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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Abstract
The invention discloses a preparation method of a T-type zeolite molecular sieve membrane, which comprises the steps of carrier tube pretreatment, seed crystal suspension preparation, dipping and crystal coating, synthetic liquid preparation and crystallization; the invention adopts a unique synthesis process, regulates the growth process of the membrane, and takes the porous alumina carrier tube, the ceramic hollow fiber tube and the mullite tube as carriers to prepare the high-performance oriented T-shaped zeolite molecular sieve membrane, thereby improving the performance and the repeatability of the molecular sieve membrane, and having higher practical value and good application prospect.
Description
Technical Field
The invention relates to the technical field of molecular sieves, in particular to a preparation method of a T-type zeolite molecular sieve membrane.
Background
The zeolite molecular sieve membrane has potential application prospect in separation under harsh environments such as high temperature, acid resistance and the like, is combined with a pervaporation technology to be applied to organic solvent dehydration in industrial production, and is expected to realize efficient and low-energy-consumption green separation. The A-type zeolite molecular sieve membrane is widely applied to industrial production all over the world, but Al atoms in a framework of the A-type zeolite molecular sieve membrane are removed under an acidic condition to cause the deterioration of membrane performance, so that the A-type zeolite molecular sieve membrane cannot be used in an acidic system. The T-type zeolite molecular sieve membrane has higher hydrophilicity and acid resistance due to the moderate silica-alumina ratio, and can be applied to separation under the condition that the A-type zeolite molecular sieve membrane cannot be applied. However, the preparation of the acid-resistant T-type zeolite molecular sieve membrane and the dehydration research make internal disorder or usurp still have many problems, which hinder the development of the industrial application. For example, the existing preparation method has the defects that the operation process is relatively complex, different heating methods such as a microwave-hydrothermal method are combined, or mineralizer fluoride ions are introduced to cause environmental pollution, or the synthesis time is too long and is more than 30h, and the like, so that the industrial application of the T-type zeolite molecular sieve membrane is limited. In addition, the preparation repeatability of the T-type zeolite molecular sieve membrane is low, and the growth mechanism of the membrane is yet to be researched. Make internal disorder or usurp people have been dedicated to improve the performance of zeolite molecular sieve membrane, improve the synthesis process and explore the growth mechanism of the membrane, but the growth mechanism of the membrane is still unclear because the membrane synthesis process usually adopts the conditions of high temperature, high pressure and hydrothermal condition, and the membrane crystal grows in the closed solution. Therefore, how to improve the synthesis process and improve the performance of the T-type zeolite molecular sieve membrane is still a difficult task.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a T-type zeolite molecular sieve membrane, which is used for solving the problems.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of a T-type zeolite molecular sieve membrane, which comprises the following steps:
pretreatment of a carrier tube: polishing the surface of the carrier tube by using sand paper, ultrasonically cleaning for half an hour, then placing the carrier tube into 0.9-1.1mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then cleaning the carrier tube by using deionized water until the surface of the carrier tube is neutral; then, placing the tube in 0.9-1.1mol/L sodium hydroxide aqueous solution for half an hour of ultrasound, and then cleaning the tube by deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 5-7h at 500-600 ℃, controlling the heating or cooling rate of the muffle furnace to be 8-12 ℃/min, and taking out for later use after calcining;
preparation of seed crystal suspension: preparing 0.8-1.2 wt% and 0.5-0.7 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively to be used as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing two ends of the pretreated carrier tube by polytetrafluoroethylene plugs, placing the carrier tube into a drying oven with the temperature of 110-; then statically curing the mixture in an oven at 180 ℃ for more than 2.5-3.5h at 170-;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; keeping the solution in a water bath kettle at a constant temperature of 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein the component of the precursor solution is SiO2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.28:0.11: 36;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
Preferably, the preparation method of the T-type zeolite molecular sieve membrane comprises the following steps:
pretreatment of a carrier tube: polishing the surface of the carrier tube by using abrasive paper, ultrasonically cleaning for half an hour, then placing the carrier tube into 1mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then cleaning the carrier tube by using deionized water until the surface of the carrier tube is neutral; then, placing the tube in 1mol/L sodium hydroxide aqueous solution for half an hour of ultrasound, and then cleaning the tube by deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 6h at 550 ℃, controlling the heating or cooling rate of the muffle furnace to be 10 ℃/min, and taking out the mixture for later use after calcining;
preparation of seed crystal suspension: preparing 1 wt% and 0.6 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively, taking the seed crystal suspension as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing two ends of the pretreated carrier tube by polytetrafluoroethylene plugs, placing the carrier tube into a 120 ℃ oven for heating for 3h, quickly immersing the preheated carrier tube into the prepared 2-micron large-crystal seed suspension liquid, taking out the carrier tube after 20s, and airing the carrier tube at room temperature overnight; then statically curing the mixture in an oven at 175 ℃ for more than 3h, taking out and cooling the mixture, then uniformly wiping off redundant seed crystals on the surface of the carrier tube by absorbent cotton, sealing two ends of the carrier tube again, placing the carrier tube into the oven at 100 ℃ for heating for 2.5h, then rapidly immersing the carrier tube into the prepared small seed crystal suspension liquid with the particle size of 600nm, taking out the carrier tube after 20s, drying the carrier tube at room temperature for 2h, and then placing the carrier tube into the oven at 100 ℃ for drying for 2.5h for later;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; keeping the solution in a water bath kettle at a constant temperature of 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein SiO in the components of the precursor solution is2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.26:0.09: 35;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
Preferably, the preparation method of the T-type zeolite molecular sieve comprises the following steps:
weighing sodium aluminate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and deionized water, putting into a glass beaker, adding a magnetic rotor, stirring strongly until the solution is clear, and continuously keeping the constant temperature of the solution in a water bath kettle at 25 ℃; adding silica sol dropwise while stirring strongly, stirring in water bath at constant temperature for 12-24 hr to obtain precursor solution of T-type zeolite molecular sieve, wherein SiO in the precursor solution2、Al2O3、Na2O、K2O、TMAOH、H2The weight ratio of O is 17.2:1:4.5:1.7:1.72: 211.7;
pouring the synthetic liquid into a reaction kettle, sealing, placing in a constant-temperature oven for static crystallization, collecting a product at the bottom of the reaction kettle, centrifugally cleaning to neutrality by using deionized water, drying, calcining at the temperature of 500-600 ℃ for 5-7h, and controlling the heating or cooling rate of the muffle furnace to be 8-12 ℃/min.
Preferably, the preparation method of the T-type zeolite molecular sieve comprises the following steps:
weighing sodium aluminate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and deionized water, putting into a glass beaker, adding a magnetic rotor, stirring strongly until the solution is clear, and continuously keeping the constant temperature of the solution in a water bath kettle at 25 ℃; dropwise adding silica sol while strongly stirring, and stirring for 18h at constant temperature in a water bath to obtain a precursor solution of the T-type zeolite molecular sieve, wherein SiO in the components of the precursor solution2、Al2O3、Na2O、K2O、TMAOH、H2The weight ratio of O is 17.2:1:4.5:1.7:1.72: 211.7;
pouring the synthetic solution into a reaction kettle, sealing, placing in a constant-temperature oven for static crystallization, collecting a product at the bottom of the reaction kettle, centrifugally cleaning with deionized water to neutrality, drying, calcining at 550 ℃ for 6h, and controlling the heating or cooling rate of a muffle furnace to be 10 ℃/min.
Preferably, the temperature of the crystallization condition in the preparation process of the 2 mu mT type zeolite molecular sieve is 120 ℃ and the time is 24 hours.
Preferably, the temperature of the crystallization condition in the preparation process of the 600nmT type zeolite molecular sieve is 100 ℃, and the time is 40 h.
Preferably, the dip coating includes:
sealing one end of the pretreated carrier tube by AB glue, connecting the other end of the carrier tube with a vacuum device, immersing the carrier tube into the prepared 2-micron large-crystal seed suspension, maintaining the vacuum degree at 0.02MPa, immersing the carrier tube for 10s, taking out the carrier tube, airing the carrier tube overnight at room temperature, then statically curing the carrier tube in an oven at 180 ℃ for more than 3h, taking out the carrier tube after cooling, uniformly wiping off redundant crystal seeds on the surface of the carrier tube by absorbent cotton, sealing one end of the hollow fiber carrier tube again, immersing the hollow fiber carrier tube into the prepared 600-nm small-crystal seed suspension, maintaining the vacuum degree at about 0.015MPa, immersing the carrier tube for 5s, then quickly taking out the carrier tube, airing the carrier tube for more than 2h at room temperature, and then drying the carrier.
Preferably, the dip coating includes:
sealing one end of a pretreated carrier tube by using AB glue, connecting the other end of the pretreated carrier tube with a vacuum device, immersing the carrier tube into the prepared 2-micron large-crystal seed suspension, maintaining the vacuum degree at 0.02MPa, immersing the carrier tube for 10s, taking out the carrier tube, airing the carrier tube overnight at room temperature, then statically curing the carrier tube in an oven at 175 ℃ for more than 3h, taking out the carrier tube after cooling, uniformly wiping off redundant crystal seeds on the surface of the carrier tube by using absorbent cotton, sealing one end of the hollow fiber carrier tube again, immersing the hollow fiber carrier tube into the prepared 600-nm small-crystal seed suspension, maintaining the vacuum degree at about 0.015MPa, immersing the hollow fiber carrier tube for 5s, then quickly taking out the hollow fiber carrier tube, airing the.
Compared with the prior art, the invention has the following beneficial effects:
the invention intervenes the shape and size of the T-type zeolite molecular sieve by regulating and controlling thermodynamic parameters influencing the crystal growth of the T-type zeolite molecular sieve and adopting unique crystallization time, crystallization temperature, alkalinity, heating mode, silica sol, feeding sequence and the like, thereby optimizing the synthesis process to obtain nano-scale seed crystals with different shapes and sizes, preparing a T-type zeolite molecular sieve membrane on a macroporous alumina carrier by adopting a two-step temperature-changing thermal dipping crystal coating method on the basis, and providing the preparation of the T-type zeolite molecular sieve membrane with a & b orientation through the epitaxial growth of membrane layer seed crystals; the appearance, the structure and the growth process of the T-type zeolite molecular sieve film layer are comprehensively interfered by regulating and controlling crystallization temperature, crystallization time and the size and the appearance of the seed crystal layer microstructure factor. Aiming at the problem that a high-quality seed crystal layer is difficult to prepare on a hollow fiber carrier, a variable-pressure vacuum impregnation crystal coating method is further adopted for crystal coating to prepare a high-performance T-type zeolite molecular sieve membrane, so that the performance and the repeatability of the molecular sieve membrane are improved, and the molecular sieve membrane has high practical value and good application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
Example 1.
The preparation method of the T-type zeolite molecular sieve membrane of the embodiment comprises the following steps:
pretreatment of a carrier tube: the carrier tube in the embodiment is a hollow fiber carrier tube, the surface of the carrier tube is polished by sand paper, and is subjected to ultrasonic cleaning for half an hour, then is placed in 0.9mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then is cleaned by deionized water until the surface of the carrier is neutral; then, placing the tube in 0.9mol/L sodium hydroxide aqueous solution for half an ultrasonic treatment, and then cleaning the tube with deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 5 hours at 500 ℃, controlling the heating or cooling rate of the muffle furnace to be 8 ℃/min, and taking out the mixture for later use after calcining;
preparation of seed crystal suspension: preparing 0.8 wt% and 0.5 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively to be used as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing two ends of the pretreated carrier tube by polytetrafluoroethylene plugs, placing the carrier tube into a drying oven at 110 ℃ for heating for 2 hours, quickly immersing the preheated carrier tube into the prepared 2-micron large-crystal seed suspension liquid, taking out the carrier tube after 18 seconds, and airing the carrier tube at room temperature overnight; then statically curing the mixture in an oven at the temperature of 170 ℃ for more than 2.5h, taking out and cooling the mixture, then uniformly wiping off redundant seed crystals on the surface of the carrier tube by absorbent cotton, sealing two ends of the carrier tube again, putting the carrier tube into the oven at the temperature of 95 ℃ for heating for 1.5h, then rapidly soaking the carrier tube into the prepared small seed crystal suspension liquid with the particle size of 600nm, taking out the carrier tube after 18s, drying the carrier tube at room temperature for 2h, and then putting the carrier tube into the oven for drying at the temperature of 95;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; keeping the solution in a water bath kettle at a constant temperature of 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein the component of the precursor solution is SiO2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.28:0.11: 36;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
The temperature of crystallization conditions in the preparation process of the 2 mu mT type zeolite molecular sieve in the embodiment is 120 ℃ and the time is 24 hours.
The temperature of crystallization conditions in the preparation process of the 600nmT type zeolite molecular sieve in the embodiment is 100 ℃, and the time is 40 h.
Example 2.
The preparation method of the T-type zeolite molecular sieve membrane of the embodiment comprises the following steps:
pretreatment of a carrier tube: polishing the surface of the carrier tube by using sand paper, ultrasonically cleaning for half an hour, then placing the carrier tube into 1.1mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then cleaning the carrier tube by using deionized water until the surface of the carrier tube is neutral; then, placing the tube in 1.1mol/L sodium hydroxide aqueous solution for half an hour of ultrasound, and then cleaning the tube by deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 7 hours at the temperature of 600 ℃, controlling the heating or cooling rate of the muffle furnace to be 12 ℃/min, and taking out the mixture for later use after calcining;
preparation of seed crystal suspension: preparing 1.2 wt% and 0.7 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively to be used as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing two ends of the pretreated carrier tube by polytetrafluoroethylene plugs, placing the carrier tube into a 130 ℃ oven for heating for 4 hours, quickly immersing the preheated carrier tube into the prepared 2-micron large-crystal seed suspension liquid, taking out the carrier tube after 22 seconds, and airing the carrier tube at room temperature overnight; then statically curing the mixture in an oven at 180 ℃ for more than 3.5h, taking out and cooling the mixture, then uniformly wiping off redundant seed crystals on the surface of the carrier tube by absorbent cotton, sealing two ends of the carrier tube again, putting the carrier tube into the oven at 105 ℃ for heating for 3.5h, then rapidly soaking the carrier tube into the prepared small seed crystal suspension liquid with the particle size of 600nm, taking out the carrier tube after 22s, drying the carrier tube at room temperature for 2h, and then putting the carrier tube into the oven at 105 ℃ for drying for 3.5h for later use;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; keeping the solution in a water bath kettle at a constant temperature of 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein the component of the precursor solution is SiO2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.28:0.11: 36;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
The temperature of crystallization conditions in the preparation process of the 2 mu mT type zeolite molecular sieve in the embodiment is 120 ℃ and the time is 24 hours.
The temperature of crystallization conditions in the preparation process of the 600nmT type zeolite molecular sieve in the embodiment is 100 ℃, and the time is 40 h.
Example 3.
The preparation method of the T-type zeolite molecular sieve membrane of the embodiment comprises the following steps:
pretreatment of a carrier tube: polishing the surface of the carrier tube by using abrasive paper, ultrasonically cleaning for half an hour, then placing the carrier tube into 1mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then cleaning the carrier tube by using deionized water until the surface of the carrier tube is neutral; then, placing the tube in 1mol/L sodium hydroxide aqueous solution for half an hour of ultrasound, and then cleaning the tube by deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 6h at 550 ℃, controlling the heating or cooling rate of the muffle furnace to be 10 ℃/min, and taking out the mixture for later use after calcining;
preparation of seed crystal suspension: preparing 1 wt% and 0.6 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively, taking the seed crystal suspension as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing two ends of the pretreated carrier tube by polytetrafluoroethylene plugs, placing the carrier tube into a 120 ℃ oven for heating for 3h, quickly immersing the preheated carrier tube into the prepared 2-micron large-crystal seed suspension liquid, taking out the carrier tube after 20s, and airing the carrier tube at room temperature overnight; then statically curing the mixture in an oven at 175 ℃ for more than 3h, taking out and cooling the mixture, then uniformly wiping off redundant seed crystals on the surface of the carrier tube by absorbent cotton, sealing two ends of the carrier tube again, placing the carrier tube into the oven at 100 ℃ for heating for 2.5h, then rapidly immersing the carrier tube into the prepared small seed crystal suspension liquid with the particle size of 600nm, taking out the carrier tube after 20s, drying the carrier tube at room temperature for 2h, and then placing the carrier tube into the oven at 100 ℃ for drying for 2.5h for later;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; maintaining the solution in the water bathKeeping the temperature at 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein SiO in the components of the precursor solution is2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.26:0.09: 35;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
The temperature of crystallization conditions in the preparation process of the 2 mu mT type zeolite molecular sieve in the embodiment is 120 ℃ and the time is 24 hours.
The temperature of crystallization conditions in the preparation process of the 600nmT type zeolite molecular sieve in the embodiment is 100 ℃, and the time is 40 h.
Example 4
This example provides a method for preparing a T-type zeolite molecular sieve, which includes the following steps:
weighing sodium aluminate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and deionized water, putting into a glass beaker, adding a magnetic rotor, stirring strongly until the solution is clear, and continuously keeping the constant temperature of the solution in a water bath kettle at 25 ℃; dropwise adding silica sol while strongly stirring, and stirring for 12h at constant temperature in a water bath to obtain a precursor solution of the T-type zeolite molecular sieve, wherein SiO in the components of the precursor solution2、Al2O3、Na2O、K2O、TMAOH、H2The weight ratio of O is 17.2:1:4.5:1.7:1.72: 211.7;
pouring the synthetic solution into a reaction kettle, sealing, placing in a constant-temperature oven for static crystallization, collecting a product at the bottom of the reaction kettle, centrifugally cleaning with deionized water to neutrality, drying, calcining at 500 ℃ for 5h, and controlling the heating or cooling rate of a muffle furnace to be 8 ℃/min.
Example 5
This example provides a method for preparing a T-type zeolite molecular sieve, which includes the following steps:
weighing sodium aluminate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and deionized water, putting into a glass beaker, adding a magnetic rotor, stirring strongly until the solution is clear, and continuously keeping the constant temperature of the solution in a water bath kettle at 25 ℃; dropwise adding silica sol while strongly stirring, and stirring for 24h at constant temperature in a water bath to obtain a precursor solution of the T-type zeolite molecular sieve, wherein SiO in the components of the precursor solution2、Al2O3、Na2O、K2O、TMAOH、H2The weight ratio of O is 17.2:1:4.5:1.7:1.72: 211.7;
pouring the synthetic solution into a reaction kettle, sealing, placing in a constant-temperature oven for static crystallization, collecting a product at the bottom of the reaction kettle, centrifugally cleaning with deionized water to neutrality, drying, calcining at 600 ℃ for 7h, and controlling the heating or cooling rate of a muffle furnace to be 12 ℃/min.
Example 6
This example provides a method for preparing a T-type zeolite molecular sieve, which includes the following steps:
weighing sodium aluminate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and deionized water, putting into a glass beaker, adding a magnetic rotor, stirring strongly until the solution is clear, and continuously keeping the constant temperature of the solution in a water bath kettle at 25 ℃; dropwise adding silica sol while strongly stirring, and stirring for 18h at constant temperature in a water bath to obtain a precursor solution of the T-type zeolite molecular sieve, wherein SiO in the components of the precursor solution2、Al2O3、Na2O、K2O、TMAOH、H2The weight ratio of O is 17.2:1:4.5:1.7:1.72: 211.7;
pouring the synthetic solution into a reaction kettle, sealing, placing in a constant-temperature oven for static crystallization, collecting a product at the bottom of the reaction kettle, centrifugally cleaning with deionized water to neutrality, drying, calcining at 550 ℃ for 6h, and controlling the heating or cooling rate of a muffle furnace to be 10 ℃/min.
Example 7
The preparation method of the T-type zeolite molecular sieve membrane of the embodiment comprises the following steps:
pretreatment of a carrier tube: polishing the surface of the carrier tube by using sand paper, ultrasonically cleaning for half an hour, then placing the carrier tube into 0.9mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then cleaning the carrier tube by using deionized water until the surface of the carrier tube is neutral; then, placing the tube in 0.9mol/L sodium hydroxide aqueous solution for half an ultrasonic treatment, and then cleaning the tube with deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 5 hours at 500 ℃, controlling the heating or cooling rate of the muffle furnace to be 8 ℃/min, and taking out the mixture for later use after calcining;
preparation of seed crystal suspension: preparing 0.8 wt% and 0.5 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively to be used as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing one end of a pretreated carrier tube by using AB glue, connecting the other end of the pretreated carrier tube with a vacuum device, immersing the carrier tube into a prepared 2-micron large-crystal seed suspension, maintaining the vacuum degree at 0.02MPa, immersing the carrier tube for 10s, taking out the carrier tube, airing the carrier tube overnight at room temperature, then statically curing the carrier tube in an oven at 170 ℃ for more than 3h, taking out the carrier tube after cooling, uniformly wiping off redundant crystal seeds on the surface of the carrier tube by using absorbent cotton, sealing one end of the hollow fiber carrier tube again, immersing the hollow fiber carrier tube into the prepared 600-nm small-crystal seed suspension, maintaining the vacuum degree at about 0.015MPa, immersing the hollow fiber carrier tube for 5s, then quickly taking out the hollow fiber carrier tube, airing the;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; keeping the solution in a water bath kettle at a constant temperature of 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein the component of the precursor solution is SiO2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.28:0.11: 36;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
The temperature of crystallization conditions in the preparation process of the 2 mu mT type zeolite molecular sieve in the embodiment is 120 ℃ and the time is 24 hours.
The temperature of crystallization conditions in the preparation process of the 600nmT type zeolite molecular sieve in the embodiment is 100 ℃, and the time is 40 h.
Example 8
The preparation method of the T-type zeolite molecular sieve membrane of the embodiment comprises the following steps:
pretreatment of a carrier tube: polishing the surface of the carrier tube by using sand paper, ultrasonically cleaning for half an hour, then placing the carrier tube into 0.9-1.1mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then cleaning the carrier tube by using deionized water until the surface of the carrier tube is neutral; then, placing the tube in 1.1mol/L sodium hydroxide aqueous solution for half an hour of ultrasound, and then cleaning the tube by deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 7 hours at the temperature of 600 ℃, controlling the heating or cooling rate of the muffle furnace to be 12 ℃/min, and taking out the mixture for later use after calcining;
preparation of seed crystal suspension: preparing 1.2 wt% and 0.7 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively to be used as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing one end of a pretreated carrier tube by using AB glue, connecting the other end of the pretreated carrier tube with a vacuum device, immersing the carrier tube into a prepared 2-micron large-crystal seed suspension, maintaining the vacuum degree at 0.02MPa, immersing the carrier tube for 10s, taking out the carrier tube, airing the carrier tube overnight at room temperature, then statically curing the carrier tube in an oven at 180 ℃ for more than 3h, taking out the carrier tube after cooling, uniformly wiping off redundant crystal seeds on the surface of the carrier tube by using absorbent cotton, sealing one end of the hollow fiber carrier tube again, immersing the hollow fiber carrier tube into the prepared 600-nm small-crystal seed suspension, maintaining the vacuum degree at about 0.015MPa, immersing the carrier tube for 5s, then quickly taking out the carrier tube, airing the carrier tube for more;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; keeping the solution in a water bath kettle at a constant temperature of 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein the component of the precursor solution is SiO2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.28:0.11: 36;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
The temperature of crystallization conditions in the preparation process of the 2 mu mT type zeolite molecular sieve in the embodiment is 120 ℃ and the time is 24 hours.
The temperature of crystallization conditions in the preparation process of the 600nmT type zeolite molecular sieve in the embodiment is 100 ℃, and the time is 40 h.
Example 9
The preparation method of the T-type zeolite molecular sieve membrane of the embodiment comprises the following steps:
pretreatment of a carrier tube: polishing the surface of the carrier tube by using abrasive paper, ultrasonically cleaning for half an hour, then placing the carrier tube into 1mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then cleaning the carrier tube by using deionized water until the surface of the carrier tube is neutral; then, placing the tube in 1mol/L sodium hydroxide aqueous solution for half an hour of ultrasound, and then cleaning the tube by deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 6h at 550 ℃, controlling the heating or cooling rate of the muffle furnace to be 10 ℃/min, and taking out the mixture for later use after calcining;
preparation of seed crystal suspension: preparing 1 wt% and 0.6 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively, taking the seed crystal suspension as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing one end of a pretreated carrier tube by using AB glue, connecting the other end of the pretreated carrier tube with a vacuum device, immersing the carrier tube into a prepared 2-micron large-crystal seed suspension, maintaining the vacuum degree at 0.02MPa, immersing the carrier tube for 10s, taking out the carrier tube, airing the carrier tube overnight at room temperature, then statically curing the carrier tube in an oven at 175 ℃, taking out the carrier tube, cooling the carrier tube, uniformly wiping off redundant crystal seeds on the surface of the carrier tube by using absorbent cotton, sealing one end of the hollow fiber carrier tube again, immersing the hollow fiber carrier tube into the prepared 600-nm small-crystal seed suspension, maintaining the vacuum degree at about 0.015MPa, immersing the carrier tube for 5s, then quickly taking out the carrier tube, airing the carrier tube for more than 2 h;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; keeping the solution in a water bath kettle at a constant temperature of 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein the component of the precursor solution is SiO2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.28:0.11: 36;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
The temperature of crystallization conditions in the preparation process of the 2 mu mT type zeolite molecular sieve in the embodiment is 120 ℃ and the time is 24 hours.
The temperature of crystallization conditions in the preparation process of the 600nmT type zeolite molecular sieve in the embodiment is 100 ℃, and the time is 40 h.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation method of a T-type zeolite molecular sieve membrane is characterized by comprising the following steps:
pretreatment of a carrier tube: polishing the surface of the carrier tube by using sand paper, ultrasonically cleaning for half an hour, then placing the carrier tube into 0.9-1.1mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then cleaning the carrier tube by using deionized water until the surface of the carrier tube is neutral; then, placing the tube in 0.9-1.1mol/L sodium hydroxide aqueous solution for half an hour of ultrasound, and then cleaning the tube by deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 5-7h at 500-600 ℃, controlling the heating or cooling rate of the muffle furnace to be 8-12 ℃/min, and taking out for later use after calcining;
preparation of seed crystal suspension: preparing 0.8-1.2 wt% and 0.5-0.7 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively to be used as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing two ends of the pretreated carrier tube by polytetrafluoroethylene plugs, placing the carrier tube into a drying oven with the temperature of 110-; then statically curing the mixture in an oven at 180 ℃ for more than 2.5-3.5h at 170-;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; keeping the solution in a water bath kettle at a constant temperature of 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein the component of the precursor solution is SiO2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.28:0.11: 36;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
2. The method for preparing a T-type zeolite molecular sieve membrane according to claim 1, wherein the method comprises the following steps:
pretreatment of a carrier tube: polishing the surface of the carrier tube by using abrasive paper, ultrasonically cleaning for half an hour, then placing the carrier tube into 1mol/L hydrochloric acid aqueous solution for ultrasonic treatment for half an hour, and then cleaning the carrier tube by using deionized water until the surface of the carrier tube is neutral; then, placing the tube in 1mol/L sodium hydroxide aqueous solution for half an hour of ultrasound, and then cleaning the tube by deionized water until the surface of the carrier is neutral; after drying, placing the mixture in a muffle furnace, calcining for 6h at 550 ℃, controlling the heating or cooling rate of the muffle furnace to be 10 ℃/min, and taking out the mixture for later use after calcining;
preparation of seed crystal suspension: preparing 1 wt% and 0.6 wt% of seed crystal suspension by sieving T-type zeolite molecules with the sizes of 2 mu m and 600nm with deionized water respectively, taking the seed crystal suspension as a large seed crystal solution and a small seed crystal solution, and dispersing the seed crystals uniformly for later use by ultrasonic dispersion for more than half an hour;
dipping and crystal coating: sealing two ends of the pretreated carrier tube by polytetrafluoroethylene plugs, placing the carrier tube into a 120 ℃ oven for heating for 3h, quickly immersing the preheated carrier tube into the prepared 2-micron large-crystal seed suspension liquid, taking out the carrier tube after 20s, and airing the carrier tube at room temperature overnight; then statically curing the mixture in an oven at 175 ℃ for more than 3h, taking out and cooling the mixture, then uniformly wiping off redundant seed crystals on the surface of the carrier tube by absorbent cotton, sealing two ends of the carrier tube again, placing the carrier tube into the oven at 100 ℃ for heating for 2.5h, then rapidly immersing the carrier tube into the prepared small seed crystal suspension liquid with the particle size of 600nm, taking out the carrier tube after 20s, drying the carrier tube at room temperature for 2h, and then placing the carrier tube into the oven at 100 ℃ for drying for 2.5h for later;
preparing a synthetic solution: weighing sodium aluminate as an aluminum source, potassium hydroxide and sodium hydroxide as alkali sources and deionized water, putting into a glass beaker, adding a magnetic rotor, and stirring strongly until the solution is clear; keeping the solution in a water bath kettle at a constant temperature of 25 ℃; after the solution is clarified, silica sol is added dropwise while strong stirring is carried out, the solution is stirred for 24 hours at constant temperature in a water bath kettle to obtain a precursor solution of the T-shaped zeolite molecular sieve membrane, wherein SiO in the components of the precursor solution is2、Al2O3、Na2O、K2O、H2The weight ratio of O is 1:0.05:0.26:0.09: 35;
and (3) crystallization: sealing two ends of a carrier tube which is dipped and coated with crystals by using a polytetrafluoroethylene plug, vertically putting the carrier tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining, slowly pouring the synthesized precursor liquid into the reaction kettle along the lining wall of the kettle, sealing, and standing for 4 hours in a constant-temperature oven at 150 ℃; taking out the stainless steel reaction kettle, placing under a tap water faucet, cooling at the highest speed, opening the kettle, taking out the membrane tube, wiping off redundant gel on the surface by using wet absorbent cotton, repeatedly washing by tap water until the surface of the membrane tube is neutral, and drying.
3. The method for preparing the T-type zeolite molecular sieve membrane according to claim 1 or 2, wherein the method for preparing the T-type zeolite molecular sieve comprises the following steps:
weighing sodium aluminate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and deionized water, putting into a glass beaker, adding a magnetic rotor, stirring strongly until the solution is clear, and continuously keeping the constant temperature of the solution in a water bath kettle at 25 ℃; adding silica sol dropwise while stirring strongly, stirring in water bath at constant temperature for 12-24 hr to obtain precursor solution of T-type zeolite molecular sieve, wherein SiO in the precursor solution2、Al2O3、Na2O、K2O、TMAOH、H2The weight ratio of O is 17.2:1:4.5:1.7:1.72: 211.7;
pouring the synthetic liquid into a reaction kettle, sealing, placing in a constant-temperature oven for static crystallization, collecting a product at the bottom of the reaction kettle, centrifugally cleaning to neutrality by using deionized water, drying, calcining at the temperature of 500-600 ℃ for 5-7h, and controlling the heating or cooling rate of the muffle furnace to be 8-12 ℃/min.
4. The method for preparing the T-type zeolite molecular sieve membrane according to claim 1 or 2, wherein the method for preparing the T-type zeolite molecular sieve comprises the following steps:
weighing sodium aluminate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and deionized water, putting into a glass beaker, adding a magnetic rotor, stirring strongly until the solution is clear, and continuously keeping the constant temperature of the solution in a water bath kettle at 25 ℃; dropwise adding silica sol while strongly stirring, and stirring for 18h at constant temperature in a water bath to obtain a precursor solution of the T-type zeolite molecular sieve, wherein SiO in the components of the precursor solution2、Al2O3、Na2O、K2O、TMAOH、H2The weight ratio of O is 17.2:1:4.5:1.7:1.72: 211.7;
pouring the synthetic solution into a reaction kettle, sealing, placing in a constant-temperature oven for static crystallization, collecting a product at the bottom of the reaction kettle, centrifugally cleaning with deionized water to neutrality, drying, calcining at 550 ℃ for 6h, and controlling the heating or cooling rate of a muffle furnace to be 10 ℃/min.
5. The method for preparing the T-type zeolite molecular sieve membrane of claim 4, wherein the temperature of the crystallization condition in the preparation process of the 2 μm T-type zeolite molecular sieve is 120 ℃ and the time is 24 h.
6. The method for preparing the T-type zeolite molecular sieve membrane of claim 4, wherein the temperature of the crystallization condition in the preparation process of the 600nm T-type zeolite molecular sieve is 100 ℃ and the time is 40 h.
7. The method for preparing a T-type zeolite molecular sieve membrane according to claim 1, wherein said dip-coating comprises:
sealing one end of the pretreated carrier tube by AB glue, connecting the other end of the carrier tube with a vacuum device, immersing the carrier tube into the prepared 2-micron large-crystal seed suspension, maintaining the vacuum degree at 0.02MPa, immersing the carrier tube for 10s, taking out the carrier tube, airing the carrier tube overnight at room temperature, then statically curing the carrier tube in an oven at 180 ℃ for more than 3h, taking out the carrier tube after cooling, uniformly wiping off redundant crystal seeds on the surface of the carrier tube by absorbent cotton, sealing one end of the hollow fiber carrier tube again, immersing the hollow fiber carrier tube into the prepared 600-nm small-crystal seed suspension, maintaining the vacuum degree at about 0.015MPa, immersing the carrier tube for 5s, then quickly taking out the carrier tube, airing the carrier tube for more than 2h at room temperature, and then drying the carrier.
8. The method for preparing a T-type zeolite molecular sieve membrane according to claim 1, wherein said dip-coating comprises:
sealing one end of a pretreated carrier tube by using AB glue, connecting the other end of the pretreated carrier tube with a vacuum device, immersing the carrier tube into the prepared 2-micron large-crystal seed suspension, maintaining the vacuum degree at 0.02MPa, immersing the carrier tube for 10s, taking out the carrier tube, airing the carrier tube overnight at room temperature, then statically curing the carrier tube in an oven at 175 ℃ for more than 3h, taking out the carrier tube after cooling, uniformly wiping off redundant crystal seeds on the surface of the carrier tube by using absorbent cotton, sealing one end of the hollow fiber carrier tube again, immersing the hollow fiber carrier tube into the prepared 600-nm small-crystal seed suspension, maintaining the vacuum degree at about 0.015MPa, immersing the hollow fiber carrier tube for 5s, then quickly taking out the hollow fiber carrier tube, airing the.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114288871A (en) * | 2021-12-31 | 2022-04-08 | 武汉智宏思博环保科技有限公司 | Method for preparing molecular sieve membrane by dip-coating molecular sieve seed crystal method |
| CN114380301A (en) * | 2022-01-27 | 2022-04-22 | 复旦大学 | Nano-sheet MFI molecular sieve and preparation method thereof |
| CN115974098A (en) * | 2023-02-15 | 2023-04-18 | 大连理工大学 | Preparation method of ultra-small nano T-type zeolite molecular sieve |
-
2020
- 2020-07-27 CN CN202010731863.1A patent/CN111760467A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114288871A (en) * | 2021-12-31 | 2022-04-08 | 武汉智宏思博环保科技有限公司 | Method for preparing molecular sieve membrane by dip-coating molecular sieve seed crystal method |
| CN114380301A (en) * | 2022-01-27 | 2022-04-22 | 复旦大学 | Nano-sheet MFI molecular sieve and preparation method thereof |
| CN115974098A (en) * | 2023-02-15 | 2023-04-18 | 大连理工大学 | Preparation method of ultra-small nano T-type zeolite molecular sieve |
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