CN110898684B - Preparation method of EMT molecular sieve membrane - Google Patents
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Abstract
The invention relates to a preparation method of an EMT molecular sieve membrane, which comprises the following steps: 1: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 Weighing aluminum source, silicon source, sodium hydroxide and template agent according to the molar ratio of (1-50) to (0.1-10) to (0-1.0) to (20-400), fully dissolving in deionized water, continuously stirring, standing and aging to obtain precursor sol; 2. immersing the pretreated ceramic support body into the precursor sol, coating the molecular sieve precursor sol on the surface of the pretreated ceramic support body by adopting a vacuum filtration process, and then drying to obtain the ceramic support body coated with the molecular sieve precursor sol; 3. and (3) placing the ceramic support body coated with the molecular sieve precursor sol in a reaction kettle with deionized water at the bottom, sealing and crystallizing, washing, drying, roasting and activating to obtain the EMT molecular sieve membrane. Compared with the prior art, the EMT molecular sieve membrane prepared by the invention has better deep removal performance when adsorbing polar oxygen-containing compound impurities in olefin flow.
Description
Technical Field
The invention belongs to the technical field of fine chemical inorganic membrane materials, and particularly relates to a preparation method and application of an EMT molecular sieve membrane.
Background
The molecular sieve membrane material is favored because of the advantages of high temperature resistance, corrosion resistance, high mechanical strength, low mass transfer resistance, large flux, uniform and adjustable pore structure and the like, and particularly has huge engineering application prospect in the field of deep purification of polar oxygen-containing compounds such as trace methanol, propionaldehyde and the like in gaseous olefin, such as a 13X molecular sieve membrane.
The EMT molecular sieve is a zeolite which has a three-dimensional twelve-membered ring channel system and is superior to an FAU topological structure, and has a more developed channel structure and better surface properties. Compared with the 13X molecular sieve, the EMT molecular sieve has better removal performance in the aspect of deep purification of polar oxygen-containing compounds such as trace methanol, propionaldehyde and the like in low-carbon olefin. Therefore, the method has many advantages and potentials in preparing the EMT molecular sieve membrane material and applying the EMT molecular sieve membrane material to the field of deep purification of gaseous olefins.
At present, the preparation of the EMT molecular sieve membrane is reported successively, and the preparation method mainly focuses on the hydrothermal crystallization method adopting a template agent. For example, patent CN 107983176 discloses a preparation method of an EMT molecular sieve membrane for separating C8 aromatic isomers. According to the method, the porous hollow fiber ceramic membrane is prepared by taking alumina as a raw material, then the surface of the ceramic membrane is pretreated by using a membrane pretreating agent, and finally a secondary growth method is adopted to prepare a plurality of layers of EMT molecular sieves on the surface of the ceramic membrane, so that the prepared EMT molecular sieve membrane has good C8 aromatic isomer separation performance, but the preparation yield of the membrane in the method cannot meet the requirement, and the raw material utilization rate is low in the preparation process of the EMT molecular sieve membrane layer. Sankhanilay et Al reported that a small-particle EMT molecular sieve with the particle size of 200 nm-1 mu m uniformly dispersed in water is used as a seed crystal, and then the seed crystal is coated on alpha-Al modified by cationic polymer poly (diallyl dimethyl ammonium chloride) 2 O 3 The EMT molecular sieve membrane with the thickness of 2 mu m is prepared after the surface and the final hydrothermal crystallization, washing, drying and roasting in the gel with the same composition, but the method has the disadvantages of complex operation, long membrane preparation time and higher raw material utilization rateLow disadvantages (Sankhanic ray Chuwdour. [ Synthesis and structural characterization of EMT-type membranes and the same Performance in nanofiltering experiments)]Journal of membrane science,2008, 314. The hydrothermal crystallization method has harsh synthesis conditions, low raw material utilization rate and film forming rate, and poor film structural integrity (poor uniformity and continuity and cracks) caused by homogeneous and heterogeneous nucleation, and seriously hinders the future industrial development of the EMT molecular sieve film. Therefore, a technology with simpler preparation process, shorter membrane preparation time, higher membrane formation rate and raw material utilization rate and more complete membrane structure is urgently needed to be developed to prepare the EMT molecular sieve membrane.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of an EMT molecular sieve membrane.
The membrane-making liquid is viscous in the preparation process of the EMT molecular sieve, and great challenges exist in the preparation of the membrane. In addition, the uniformity, continuity, integrity, strong and weak binding force and the like of the EMT molecular sieve membrane have great influence on the deep purification performance of the gaseous olefin. Therefore, how to prepare the EMT molecular sieve membrane which is continuous, compact, uniform in thickness, free of cracks, narrow in pore size distribution and strong in binding force becomes a key point.
The invention adopts a steam crystallization method to prepare the EMT molecular sieve membrane, solves the technical problem of membrane preparation in high-viscosity sol solution, and particularly adopts a method combining steam crystallization, surface modification and vacuum coating to prepare the EMT molecular sieve membrane, so that on one hand, a compact and continuous EMT molecular sieve membrane layer without cracks and with strong binding force can be obtained, on the other hand, the preparation process can be simplified, the membrane preparation time can be shortened, the membrane forming rate and the raw material utilization rate can be improved, and the cost can be reduced to the maximum extent.
The purpose of the invention can be realized by the following technical scheme: the preparation method of the EMT molecular sieve membrane is characterized by comprising the following steps:
step one, sol preparation: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 The molar ratio of O is 1 (1-50) to 0.1-10 to 0-1.0) Weighing aluminum source, silicon source, sodium hydroxide and template agent according to the proportion of (20-400), fully dissolving in deionized water, continuously stirring for 1-12 h, and then standing and aging for 12-72 h at 5-80 ℃ to obtain precursor sol;
step two, sol coating: immersing the pretreated ceramic support body into the precursor sol, coating the molecular sieve precursor sol on the surface of the pretreated ceramic support body by adopting a vacuum filtration process, and then drying for 1-48 h at the temperature of 25-90 ℃ to obtain the ceramic support body coated with the molecular sieve precursor sol;
step three, steam crystallization: and (2) placing the ceramic support body coated with the molecular sieve precursor sol into a reaction kettle with deionized water at the bottom, sealing and crystallizing for 1-20 days at 100-180 ℃, then washing until the pH value is 7-8, drying for 1-8 h at 110-150 ℃, and finally roasting and activating for 1-10 h at 450-750 ℃ to obtain the EMT molecular sieve membrane.
The specific process for preparing the sol in the step one is as follows: respectively weighing an aluminum source, a silicon source, sodium hydroxide, a template agent and deionized water, then fully dissolving the aluminum source into a sodium hydroxide solution under stirring, then adding the silicon source and the template agent into the aluminum solution, finally continuously stirring for 2-8 h, standing and aging for 12-48 h to obtain precursor sol; wherein the adding amount of the aluminum source, the silicon source, the sodium hydroxide, the template agent and the deionized water is according to the Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 The molar ratio of O is preferably 1:3-20.
The aluminum source comprises one or more of aluminum hydroxide, hydrated alumina, alumina sol, sodium aluminate, aluminum isopropoxide or bauxite;
the silicon source comprises one or more of solid silica gel, solid sodium silicate, water glass, silica sol, tetraethyl silicate, methyl orthosilicate, ethyl orthosilicate and white carbon black;
the template agent is one or a mixture of 15-crown-5 ether, 18-crown-6 ether, polyethylene glycol or polyquaternium-6. In particular, the template agent is preferably 15-crown-5 ether or 18-crown-6 ether or a mixture of the two.
As a preferable embodiment, the temperature of the sol in the step one is 15-40 ℃, and the aging time is 18-36 h.
The ceramic support body in the second step is a tubular porous support body with a single-channel or multi-channel structure, and is made of alumina, zirconia or titanium oxide;
preferably, the ceramic support has an average pore diameter of 1 to 3 μm, a porosity of 30 to 45%, an outer diameter of 12 to 100mm, and an inner diameter of 3 to 50mm.
The method for coating the molecular sieve precursor sol on the surface of the pretreated ceramic support in the second step specifically comprises the following steps: uniformly stirring the molecular sieve precursor sol, then plugging one end of a tubular ceramic support body, connecting the other end of the tubular ceramic support body with a vacuum pump, vertically immersing the tubular ceramic support body in the molecular sieve precursor sol, keeping the vacuum degree in the tubular ceramic support body at 0.0001-0.005 MPa, performing suction filtration for 5 s-10 min, then taking the tubular ceramic support body out of the molecular sieve precursor sol, removing the redundant sol on the surface of the support body, and placing the support body in a drying oven at 40-85 ℃ for 2-24 h.
The pretreatment of the ceramic support body in the second step comprises the following steps: firstly, using 100-500 mesh sand paper to carry out rough grinding, then using 1200-2500 mesh sand paper to carry out fine grinding, carrying out ultrasonic cleaning by acetone, drying, roasting at 200-500 ℃ for 0.5-10 h, and finally soaking the roasted ceramic support body in 0.1-10 wt% of poly (diallyldimethylammonium chloride) solution to carry out surface modification for 1-10 h. The surface of the ceramic support is modified by adopting the cationic polymer, so that the roughness of the surface of the ceramic support is optimized, rich groups are formed on the surface of the modified ceramic support, the hydrophilicity and the electronegativity of the surface of the ceramic support are obviously improved, and the loading capacity of the molecular sieve crystal seeds is effectively ensured.
The steam crystallization process in the third step is as follows: placing the ceramic support body coated with the molecular sieve precursor at the upper end of a reaction kettle with a net-shaped interlayer, then filling deionized water at the bottom, and finally carrying out closed crystallization at 110-150 ℃ for 3-7 days;
the deionized water dosage at the bottom of the reaction kettle is determined according to the dried molecular sieve precursor dosage coated on the surface of the ceramic support body, and the specific dosage is as follows: the mass ratio of the deionized water to the molecular sieve precursor is 1:1-1.
The thickness of the molecular sieve membrane layer of the prepared EMT molecular sieve membrane is 3.0 mu m, the particle size of the EMT molecular sieve in the molecular sieve layer is 1.0 mu m, and the average pore size of the molecular sieve is 1.3-2.0 nm.
The EMT molecular sieve membrane is used for deeply removing polar oxygen-containing compound impurities in a gaseous olefin flow to below 1ppm, and the removal performance of the EMT molecular sieve membrane is far superior to that of the existing gaseous olefin flow purification material.
The use method of the EMT molecular sieve membrane comprises the following steps: installing a tubular EMT molecular sieve ceramic membrane material in a membrane module, sealing two ends of the molecular sieve ceramic membrane by using epoxy silicone rings, and activating the installed EMT molecular sieve ceramic membrane before the first use; then, allowing the gaseous olefin containing trace polar oxygen-containing compound impurities such as methanol, propionaldehyde and the like to flow through the membrane side of the EMT molecular sieve ceramic membrane material, and allowing the adsorbed and purified permeate gas to flow out from the other side of the membrane, thus obtaining the purified gaseous olefin. After an adsorption period is finished, hot nitrogen or methane hydrogen can be adopted for blowing and regenerating, and the regenerated tail gas is directly discharged or the flare gas is removed.
The invention provides an EMT molecular sieve membrane prepared by a steam crystallization method, which comprises the steps of firstly coating a molecular sieve precursor sol on the surface of a ceramic support body, then placing the dried ceramic support body coated with the molecular sieve precursor sol in a reaction kettle with deionized water at the bottom for closed crystallization, and thus obtaining the EMT molecular sieve membrane. When the EMT molecular sieve membrane is applied to deep purification of polar oxygen-containing compounds such as trace methanol, propionaldehyde and the like in gaseous olefin, the content of impurities can be removed to be below 1ppm, and the removal performance of the EMT molecular sieve membrane is far superior to that of the existing gaseous olefin stream purification material. In addition, the EMT molecular sieve membrane has small mass transfer resistance, low energy consumption and strong regeneration capacity, so that the EMT molecular sieve membrane can realize long-period continuous operation in the deep purification of gaseous olefins.
Although the film-forming solution (i.e., precursor sol) is viscous in the preparation process of the EMT molecular sieve, the invention firstly pretreats the ceramic support to ensure that the surface of the ceramic support can be well combined with the precursor sol, then adopts a vacuum coating process to ensure that the viscous precursor sol can form a uniform, continuous and complete precursor film layer on the ceramic support, and the dried precursor can be directly transformed into the EMT molecular sieve in a steam environment, thereby synthesizing the EMT molecular sieve film with better uniformity, continuity and integrity, stronger binding force and narrower pore size distribution. The EMT molecular sieve membrane has excellent mechanical strength, low mass transfer resistance and high heat resistance, and simultaneously has excellent deep purification performance of polar oxygen-containing compounds such as trace methanol, propionaldehyde and the like in gaseous olefins, which is far superior to the existing material. In addition, the EMT molecular sieve membrane material also has lower regeneration temperature and stronger regeneration reusability.
Compared with the prior art, the invention has the following characteristics:
1) Compared with the prior EMT molecular sieve membrane preparation technology, the invention adopts the steam crystallization technology to prepare the EMT molecular sieve membrane for the first time, and directly converts the xerogel layer into the EMT molecular sieve layer, thereby avoiding membrane defects caused by homogeneous and heterogeneous nucleation and the like in the contact with the crystallization liquid; in addition, the preparation process is simplified, the film forming time is shortened, and the film forming rate and the raw material utilization rate are improved.
2) The combination of steam crystallization, surface modification and vacuum coating technology solves the technical problem of membrane preparation in high-viscosity sol solution, and further ensures the structural integrity of the prepared EMT molecular sieve membrane.
3) Compared with the prior EMT molecular sieve membrane, the EMT molecular sieve membrane prepared by the invention has high mechanical strength, strong binding force between the EMT molecular sieve and the ceramic support body, compact, continuous and uniform EMT molecular sieve loaded on the surface of the ceramic support body, the thickness of the molecular sieve membrane layer is 3.0 mu m, the particle size of the EMT molecular sieve in the molecular sieve layer is 1.0 mu m, and the average pore size of the molecular sieve is 1.3-2.0 nm. When the method is applied to the deep purification of the polar oxygen-containing compound impurities in the gaseous olefin flow, the impurities can be deeply removed to be below 1ppm, and the removal performance of the method is far superior to that of the existing gaseous olefin flow purification material.
4) Compared with the prior art for deeply purifying the polar oxygen-containing compound impurities in the gaseous olefin, the EMT molecular sieve membrane prepared by the invention not only meets the requirements on purification depth and performance, but also has small filling volume, low mass transfer resistance and low loss, and has low regeneration energy consumption and high reuse efficiency when being repeatedly used, and can realize long-period continuous operation in the deep purification of the polar oxygen-containing compounds such as trace methanol, propionaldehyde and the like in the gaseous olefin.
5) The process for preparing the EMT molecular sieve membrane by the steam crystallization method is simple and stable, the investment cost of the device at the early stage is low, and industrialization is easy to realize.
Drawings
FIG. 1 is an XRD pattern of EMT molecular sieve particles on the surface of the EMT molecular sieve membrane prepared in example 1;
FIG. 2 is a sectional SEM photograph of the EMT molecular sieve membrane prepared in example 1;
FIG. 3 is a surface SEM photograph of the EMT molecular sieve membrane prepared in example 1;
fig. 4 is an adsorption breakthrough curve of the EMT molecular sieve membrane prepared in example 1 for methanol and propionaldehyde impurities in an ethylene system: 13X molecular sieve membrane as control group;
fig. 5 is an adsorption breakthrough curve of the EMT molecular sieve membrane prepared in example 2 for methanol and propionaldehyde impurities in an ethylene system.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreatment of the ceramic support body: single-channel alpha-Al with the average aperture of 1 mu m, the porosity of 30 percent, the outer diameter of 12mm and the inner diameter of 8mm 2 O 3 The ceramic tube is cut into short tubes of 40mm, thenAnd then, sequentially polishing and smoothing by using 280-mesh and 1500-mesh abrasive paper, then sequentially ultrasonically cleaning by using acetone and deionized water for 1h, drying in a 110-DEG C oven for 4h, finally roasting in a 200-DEG C muffle furnace for 10h, naturally cooling to room temperature, finally soaking the ceramic support in a 1wt% poly (diallyldimethylammonium chloride) solution for 5min, taking out, washing off the excessive poly (diallyldimethylammonium chloride) on the surface by using the deionized water, and drying at 50 ℃ for 2 h.
Preparing sol: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 Weighing sodium aluminate, silica sol, sodium hydroxide, 15-crown-5 ether and water according to the molar ratio of 1. Firstly, dissolving sodium aluminate in a sodium hydroxide solution, then respectively adding silica sol and 15-crown-5 ether into an aluminum solution under continuous stirring, continuing stirring for 1h, and then standing and aging at 20 ℃ for 36h to obtain precursor sol.
Coating sol: one end of the pretreated ceramic support body (ceramic tube) is blocked, the other end of the pretreated ceramic support body (ceramic tube) is connected with a vacuum pump, then the ceramic tube is vertically immersed in the newly-prepared precursor sol, the ceramic tube is subjected to suction filtration for 5s under the vacuum degree of 0.0001MPa in the tube, the ceramic tube is slowly taken out of the sol, the excessive sol on the surface is removed by using filter paper, the two ends of the ceramic tube are tightly plugged by using a plug, and the ceramic tube is placed in a 40 ℃ oven for pretreatment for 24 hours for standby.
Steam crystallization: and (2) placing the ceramic support body coated with the molecular sieve precursor sol into a reaction kettle with deionized water at the bottom (the dosage ratio of the deionized water to the molecular sieve precursor sol is 1:1), sealing and crystallizing for 7 days at 100 ℃, then washing until the pH value is 7-8, drying for 8 hours at 110 ℃, and finally roasting for 4 hours at 450 ℃ to obtain the EMT molecular sieve membrane.
Fig. 1 is an XRD chart of the EMT molecular sieve particles on the surface of the prepared EMT molecular sieve membrane, and the result shows that the EMT molecular sieve with higher crystallinity can be prepared by the steam crystallization method as well. FIG. 2 is a sectional view of the EMT molecular sieve membrane prepared on the surface of the EMT molecular sieve membrane, and the membrane thickness is about 3.0 μm. The penetration curve (the operating pressure is 0.3MPa, and the total flow is 100 ml/min) of the EMT molecular sieve membrane used for polar oxygen-containing compound impurities of trace methanol and propionaldehyde in ethylene shows that the EMT molecular sieve membrane can deeply remove the trace methanol and propionaldehyde to be below 1ppm, and has better olefin deep purification performance than a 13X molecular sieve membrane. The adsorption breakthrough time of the EMT molecular sieve membrane on methanol is 116h, and the adsorption breakthrough time on propionaldehyde is 200h, which is shown in figure 3.
Example 2
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreatment of the ceramic support body: subjecting single-channel alpha-Al with average pore diameter of 3 μm, porosity of 45%, outer diameter of 100mm and inner diameter of 50mm to vacuum distillation 2 O 3 Cutting the ceramic tube into short tubes of 45mm, polishing and smoothing by using abrasive paper of 100 meshes and 2500 meshes in sequence, ultrasonically cleaning by using acetone and deionized water for 1h, drying in a 110 ℃ oven for 4h, roasting in a 500 ℃ muffle furnace for 0.5h, naturally cooling to room temperature for later use, and finally, placing in a 0.1wt% poly (diallyldimethylammonium chloride) solution for surface modification.
Sol preparation: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 Weighing sodium aluminate, silica sol, sodium hydroxide, 15-crown-5 ether and water according to the molar ratio of 1. Firstly, dissolving sodium aluminate in a sodium hydroxide solution, then respectively adding silica sol and 15-crown-5 ether into an aluminum solution under continuous stirring, continuing stirring for 12 hours, and then standing and aging at 40 ℃ for 18 hours to obtain precursor sol.
Coating sol: one end of the pretreated ceramic support body (ceramic tube) is blocked, the other end of the pretreated ceramic support body (ceramic tube) is connected with a vacuum pump, then the ceramic tube is vertically immersed in the newly-prepared precursor sol, suction filtration is carried out for 10min under the vacuum degree of 0.005MPa in the tube, the ceramic tube is slowly taken out of the gel, the excessive sol on the surface is removed by using filter paper, the two ends of the ceramic tube are tightly plugged by using plugs, and the ceramic tube is placed in an oven at 85 ℃ for pretreatment for 2h for standby.
Steam crystallization: placing the ceramic support body coated with the molecular sieve precursor sol into a reaction kettle with deionized water at the bottom (the dosage ratio of the deionized water to the molecular sieve precursor sol is 1 to 60), sealing and crystallizing for 3 days at 100 ℃, then washing to pH 7-8, drying for 1h at 150 ℃, and finally roasting for 4h at 550 ℃ to obtain the EMT molecular sieve membrane.
The penetration curve (the operating pressure is 0.3MPa, and the total flow is 100 ml/min) of the EMT molecular sieve membrane used for polar oxygen-containing compound impurities of trace methanol and propionaldehyde in ethylene shows that the EMT molecular sieve membrane can deeply remove the trace methanol and propionaldehyde to be below 1ppm, and has better olefin deep purification performance than a 13X molecular sieve membrane. The adsorption breakthrough time of the EMT molecular sieve membrane on methanol is 114h, and the adsorption breakthrough time on propionaldehyde is 198h, as shown in figure 4.
Example 3
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreatment of the ceramic support body: subjecting single-channel alpha-Al with average pore diameter of 3 μm, porosity of 40%, outer diameter of 50mm and inner diameter of 10mm to vacuum distillation 2 O 3 Cutting the ceramic tube into short tubes of 50mm, polishing and smoothing the short tubes by using sand paper of 120 meshes and 2000 meshes in sequence, ultrasonically cleaning the short tubes for 2 hours by using acetone and deionized water in sequence, drying the short tubes in a baking oven at the temperature of 140 ℃ for 4 hours, roasting the short tubes in a muffle furnace at the temperature of 600 ℃ for 2 hours, naturally cooling the short tubes to room temperature for later use, and finally, placing the short tubes in 10wt% polydiallyl dimethyl ammonium chloride solution for surface modification.
Sol preparation: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 Weighing sodium aluminate, silica sol, sodium hydroxide, 18-crown-6 ether and water according to the molar ratio of 1. Firstly, dissolving sodium aluminate in a sodium hydroxide solution, then respectively adding silica sol and 18-crown-6 ether into an aluminum solution under continuous stirring, continuously stirring for 4 hours, and then standing and aging for 24 hours at 30 ℃ to obtain precursor sol.
Coating sol: one end of the pretreated ceramic support body (ceramic tube) is blocked, the other end of the ceramic support body (ceramic tube) is connected with a vacuum pump, then the ceramic tube is vertically immersed in the newly-prepared precursor sol, the ceramic tube is subjected to suction filtration for 10min under the vacuum degree of 0.005MPa in the tube, the ceramic tube is slowly taken out of the gel, the excessive sol on the surface is removed by using filter paper, the two ends of the ceramic tube are tightly plugged by using a plug, and the ceramic tube is placed in an oven at 85 ℃ for pretreatment for 2h for standby.
Steam crystallization: and (2) placing the ceramic support body coated with the molecular sieve precursor sol into a reaction kettle with deionized water at the bottom (the dosage ratio of the deionized water to the molecular sieve precursor sol is 1: 30), sealing and crystallizing for 7 days at 110 ℃, then washing to pH 7-8, drying for 6h at 130 ℃, and finally roasting for 4h at 550 ℃ to obtain the EMT molecular sieve membrane.
The bending strength of the EMT molecular sieve membrane is 23MPa, the binding force between the EMT molecular sieve and the ceramic support body is 17N, the EMT molecular sieve loaded on the surface of the ceramic support body is dense, continuous and uniform, the thickness of the molecular sieve membrane layer is 1.0 mu m, the particle size of the EMT molecular sieve in the molecular sieve layer is 1.0 mu m, and the average pore size of the molecular sieve is 1.5nm. When the method is applied to the deep purification of the polar oxygen-containing compound impurities in the gaseous olefin flow, the impurities can be deeply removed to be below 1ppm, and the removal performance of the method is far superior to that of the existing gaseous olefin flow purification material.
Example 4
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreatment of the ceramic support body: single-channel ZrO having an average pore diameter of 3 μm, a porosity of 40%, an outer diameter of 50mm and an inner diameter of 10mm was subjected to hot melt extrusion 2 Cutting the ceramic tube into short tubes of 50mm, polishing and smoothing the short tubes by using sand paper of 200 meshes and 2000 meshes in sequence, ultrasonically cleaning the short tubes for 2h by using acetone and deionized water in sequence, drying the short tubes in an oven at the temperature of 140 ℃ for 4h, roasting the short tubes in a muffle furnace at the temperature of 300 ℃ for 2h, naturally cooling the short tubes to room temperature, soaking the ceramic support in a 3wt% polydiallyl dimethyl ammonium chloride solution for 5min, taking out the ceramic support, washing off redundant polydiallyl dimethyl ammonium chloride on the surface by using deionized water, and drying the ceramic support for 2h at the temperature of 50 ℃.
Sol preparation: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 Weighing sodium aluminate, silica sol, sodium hydroxide, 18-crown-6 ether and water according to the molar ratio of 1. Firstly, dissolving sodium aluminate in a sodium hydroxide solution, then respectively adding silica sol and 18-crown-6 ether into an aluminum solution under continuous stirring, continuing stirring for 8 hours, and then standing and aging for 20 hours at 25 ℃ to obtain precursor sol.
Coating sol: and (3) plugging one end of the pretreated ceramic support body (ceramic tube), connecting the other end of the pretreated ceramic support body (ceramic tube) with a vacuum pump, vertically immersing the ceramic tube in the newly prepared precursor sol, carrying out suction filtration for 1min under the vacuum degree of 0.0001MPa in the tube, slowly taking the ceramic tube out of the gel, removing the redundant sol on the surface by using filter paper, plugging the two ends by using plugs, and placing the ceramic tube in an oven at 85 ℃ for pretreatment for 1h for later use.
Steam crystallization: placing the ceramic support body coated with the molecular sieve precursor sol into a reaction kettle with deionized water at the bottom (the dosage ratio of the deionized water to the molecular sieve precursor sol is 1: 30), sealing and crystallizing at 110 ℃ for 7 days, then washing to pH 7-8, drying at 130 ℃ for 4h, and finally roasting at 550 ℃ for 4h to obtain the EMT molecular sieve membrane.
The bending strength of the EMT molecular sieve membrane is 30MPa, the binding force between the EMT molecular sieve and the ceramic support body is 28N, the EMT molecular sieve loaded on the surface of the ceramic support body is dense, continuous and uniform, the thickness of the molecular sieve membrane layer is 2.0 mu m, the particle size of the EMT molecular sieve in the molecular sieve layer is 0.5 mu m, and the average pore size of the molecular sieve is 1.8nm. When the method is applied to the deep purification of the polar oxygen-containing compound impurities in the gaseous olefin flow, the impurities can be deeply removed to be below 1ppm, and the removal performance of the method is far superior to that of the existing gaseous olefin flow purification material.
Example 5
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreatment of the ceramic support body: single-channel TiO with the average aperture of 3 mu m, the porosity of 45 percent, the outer diameter of 12mm and the inner diameter of 8mm 2 Cutting the ceramic tube into short tubes of 40mm, polishing with sand paper of 250 meshes and 2500 meshes in sequence to be smooth, ultrasonically cleaning with acetone and deionized water for 2h in a baking oven at 140 ℃, drying for 4h, finally roasting in a muffle furnace at 200 ℃ for 2h, naturally cooling to room temperature, finally soaking the ceramic support body in 8wt% polydiallyl dimethyl ammonium chloride solution for 5min, taking out, washing off excessive polydiallyl dimethyl ammonium chloride on the surface with deionized water, and drying for 2h at 50 ℃.
Sol preparation: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 Weighing sodium aluminate and the following components in a molar ratio of 1Silica sol, sodium hydroxide, 18-crown-6 ether and water. Firstly, dissolving sodium aluminate in a sodium hydroxide solution, then respectively adding silica sol and 18-crown-6 ether into an aluminum solution under continuous stirring, continuing stirring for 8 hours, and then standing and aging at 25 ℃ for 36 hours to obtain precursor sol.
Coating sol: one end of the pretreated ceramic support body (ceramic tube) is blocked, the other end of the pretreated ceramic support body (ceramic tube) is connected with a vacuum pump, then the ceramic tube is vertically immersed in the newly-prepared precursor sol, the ceramic tube is subjected to suction filtration for 1min under the vacuum degree of 0.0001MPa in the tube, the ceramic tube is slowly taken out of the gel, the excessive sol on the surface is removed by using filter paper, the two ends of the ceramic tube are tightly plugged by using plugs, and the ceramic tube is placed in a 60 ℃ oven for pretreatment for 3h for standby.
Steam crystallization: and (2) placing the ceramic support body coated with the molecular sieve precursor sol into a reaction kettle with deionized water at the bottom (the dosage ratio of the deionized water to the molecular sieve precursor sol is 1: 30), sealing and crystallizing for 5 days at 110 ℃, then washing to pH 7-8, drying for 4h at 130 ℃, and finally roasting for 4h at 550 ℃ to obtain the EMT molecular sieve membrane.
The bending strength of the EMT molecular sieve membrane is 28MPa, the binding force between the EMT molecular sieve and the ceramic support body is 24N, the EMT molecular sieve loaded on the surface of the ceramic support body is dense, continuous and uniform, the thickness of the molecular sieve membrane layer is 3.0 mu m, the particle size of the EMT molecular sieve in the molecular sieve layer is 0.3 mu m, and the average pore size of the molecular sieve is 1.3nm. When the method is applied to the deep purification of the polar oxygen-containing compound impurities in the gaseous olefin flow, the impurities can be deeply removed to be below 1ppm, and the removal performance of the method is far superior to that of the existing gaseous olefin flow purification material.
Example 6
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreatment of the ceramic support body: subjecting single-channel alpha-Al with average pore diameter of 2 μm, porosity of 45%, outer diameter of 12mm and inner diameter of 8mm to vacuum distillation 2 O 3 Cutting the ceramic tube into 45mm short tubes, polishing with 250 mesh and 2500 mesh abrasive paper, ultrasonic cleaning with acetone and deionized water for 2 hr, drying in 150 deg.C oven for 2 hr, calcining in 250 deg.C muffle furnace for 3 hr, naturally cooling to room temperatureThen the mixture is finally placed into a 5wt% polydiallyldimethylammonium chloride solution for surface modification.
Sol preparation: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 Weighing sodium aluminate, silica sol, sodium hydroxide, 18-crown-6 ether and water according to the molar ratio of 1. Firstly, dissolving sodium aluminate in a sodium hydroxide solution, then respectively adding silica sol and 18-crown-6 ether into an aluminum solution under continuous stirring, continuing stirring for 8 hours, and then standing and aging for 36 hours at 40 ℃ to obtain precursor sol.
Coating sol: and (3) plugging one end of the pretreated ceramic support body (ceramic tube), connecting the other end of the pretreated ceramic support body (ceramic tube) with a vacuum pump, vertically immersing the ceramic tube in the newly prepared precursor sol, carrying out suction filtration for 2min under the vacuum degree of 0.0001MPa in the tube, slowly taking the ceramic tube out of the gel, removing the redundant sol on the surface by using filter paper, plugging the two ends by using plugs, and placing the ceramic tube in a 50 ℃ oven for pretreatment for 3h for later use.
Steam crystallization: placing the ceramic support body coated with the molecular sieve precursor sol into a reaction kettle with deionized water at the bottom (the dosage ratio of the deionized water to the molecular sieve precursor sol is 1: 30), sealing and crystallizing at 110 ℃ for 7 days, then washing to pH 7-8, drying at 130 ℃ for 4h, and finally roasting at 550 ℃ for 4h to obtain the EMT molecular sieve membrane.
The bending strength of the EMT molecular sieve membrane is 27MPa, the binding force between the EMT molecular sieve and the ceramic support body is 22N, the EMT molecular sieve loaded on the surface of the ceramic support body is dense, continuous and uniform, the thickness of the molecular sieve membrane layer is 1.5 mu m, the particle size of the EMT molecular sieve in the molecular sieve layer is 0.8 mu m, and the average pore size of the molecular sieve is 1.8nm. When the method is applied to the deep purification of the polar oxygen-containing compound impurities in the gaseous olefin flow, the impurities can be deeply removed to be below 1ppm, and the removal performance of the method is far superior to that of the existing gaseous olefin flow purification material.
Example 7
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreatment of the ceramic support body: cutting a multichannel zirconia ceramic tube with the average pore diameter of 2 mu m, the porosity of 35 percent, the outer diameter of 80mm and the inner diameter of 20mm into short tubes with the diameter of 45mm, then sequentially polishing the short tubes with sand paper with the meshes of 100 and 1200, then sequentially ultrasonically cleaning the short tubes with acetone and deionized water for 2 hours, drying the short tubes in an oven with the temperature of 110 ℃ for 2 hours, placing the short tubes in a muffle furnace with the temperature of 200 ℃ for roasting for 10 hours, naturally cooling the short tubes to the room temperature for standby, and finally placing the short tubes in a polydiallyldimethylammonium chloride solution with the weight percent of 3 percent for surface modification.
Sol preparation: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 The molar ratio of O is 1. Firstly, dissolving sodium aluminate in a sodium hydroxide solution, then respectively adding silica sol and 18-crown-6 ether into an aluminum solution under continuous stirring, continuously stirring for 1h, and then standing and aging at 80 ℃ for 12h to obtain precursor sol.
Coating sol: blocking one end of a pretreated ceramic support (ceramic tube), connecting the other end of the pretreated ceramic support (ceramic tube) with a vacuum pump, vertically immersing the ceramic tube in the newly prepared precursor sol, carrying out suction filtration for 5s under the pressure of 0.0001MPa in the tube, slowly taking the ceramic tube out of the gel, removing excessive sol on the surface by using filter paper, tightly blocking the two ends by using plugs, and placing the ceramic tube in an oven at 40 ℃ for keeping for 24 hours for later use.
Steam crystallization: placing the ceramic support body coated with the molecular sieve precursor sol into a reaction kettle with deionized water at the bottom (the dosage ratio of the deionized water to the molecular sieve precursor sol is 1:1), sealing and crystallizing for 20 days at 100 ℃, then washing until the pH value is 7-8, drying for 8h at 110 ℃, and finally roasting and activating for 10h at 450 ℃ to obtain the EMT molecular sieve membrane.
The bending strength of the EMT molecular sieve membrane is 22MPa, the binding force between the EMT molecular sieve and the ceramic support body is 18N, the EMT molecular sieve loaded on the surface of the ceramic support body is dense, continuous and uniform, the thickness of the molecular sieve membrane layer is 1.0 mu m, the particle size of the EMT molecular sieve in the molecular sieve layer is 1.0 mu m, and the average pore size of the molecular sieve is 1.5nm. When the method is applied to the deep purification of the polar oxygen-containing compound impurities in the gaseous olefin flow, the impurities can be deeply removed to be below 1ppm, and the removal performance of the method is far superior to that of the existing gaseous olefin flow purification material.
Example 8
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreatment of the ceramic support body: single-channel alpha-Al with the average aperture of 2 mu m, the porosity of 45 percent, the outer diameter of 12mm and the inner diameter of 8mm is prepared 2 O 3 Cutting the ceramic tube into short tubes of 45mm, polishing with sand paper of 250 meshes and 2500 meshes in sequence, ultrasonically cleaning with acetone and deionized water for 2h, drying in an oven at 150 ℃ for 2h, roasting in a muffle furnace at 250 ℃ for 3h, naturally cooling to room temperature for later use, and finally placing in a 5wt% poly (diallyldimethylammonium chloride) solution for surface modification.
Sol preparation: according to Al 2 O 3 :SiO 2 :Na 2 O is a template agent H 2 Weighing aluminum hydroxide, solid silica gel, sodium hydroxide, polyethylene glycol and water according to the molar ratio of 1. Firstly, dissolving sodium aluminate in a sodium hydroxide solution, then respectively adding silica sol and 18-crown-6 ether into an aluminum solution under continuous stirring, continuously stirring for 12h, and then standing and aging for 72h at 5 ℃ to obtain precursor sol.
Coating sol: and (3) plugging one end of the pretreated ceramic support body (ceramic tube), connecting the other end of the pretreated ceramic support body (ceramic tube) with a vacuum pump, vertically immersing the ceramic tube in the newly prepared precursor sol, performing suction filtration for 10min at 0.005MPa in the tube, slowly taking the ceramic tube out of the gel, removing the redundant sol on the surface by using filter paper, plugging the two ends by using plugs, and placing the ceramic tube in an oven at 85 ℃ for 2h for later use.
Steam crystallization: placing the ceramic support body coated with the molecular sieve precursor sol into a reaction kettle with deionized water at the bottom (the dosage ratio of the deionized water to the molecular sieve precursor sol is 1 to 60), sealing and crystallizing for 1 day at 180 ℃, then washing to pH 7-8, drying for 1h at 150 ℃, and finally roasting and activating for 1h at 750 ℃ to obtain the EMT molecular sieve membrane.
The bending strength of the EMT molecular sieve membrane is 25MPa, the binding force between the EMT molecular sieve and the ceramic support body is 20N, the EMT molecular sieve loaded on the surface of the ceramic support body is dense, continuous and uniform, the thickness of the molecular sieve membrane layer is 3.0 mu m, the particle size of the EMT molecular sieve in the molecular sieve layer is 1.0 mu m, and the average pore size of the molecular sieve is 2nm. When the method is applied to the deep purification of the polar oxygen-containing compound impurities in the gaseous olefin flow, the impurities can be deeply removed to be below 1ppm, and the removal performance of the method is far superior to that of the existing gaseous olefin flow purification material.
Claims (9)
1. The preparation method of the EMT molecular sieve membrane is characterized by comprising the following steps:
step one, sol preparation: according to Al 2 O 3 : SiO 2 : Na 2 O is a template agent H 2 The molar ratio of O is 1: (1-50) weighing aluminum source, silicon source, sodium hydroxide and template agent according to the proportion of (0.1-10) to (0-1.0) to (20-400), fully dissolving in deionized water, continuously stirring for 1-12 h, and then standing and aging for 12-72 h at 5-80 ℃ to obtain precursor sol;
step two, sol coating: immersing the pretreated ceramic support body into the precursor sol, and coating the surface of the pretreated ceramic support body with the molecular sieve precursor sol by adopting a vacuum filtration process: uniformly stirring the molecular sieve precursor sol, then plugging one end of a tubular ceramic support body, connecting the other end of the tubular ceramic support body with a vacuum pump, vertically immersing the tubular ceramic support body in the molecular sieve precursor sol, keeping the vacuum degree in the tubular ceramic support body at 0.0001-0.005 MPa, performing suction filtration for 5 s-10 min, then taking the tubular ceramic support body out of the molecular sieve precursor sol, removing the redundant sol on the surface of the support body, and then drying at 25-90 ℃ for 1-48 h to obtain the ceramic support body coated with the molecular sieve precursor sol; the pretreatment of the ceramic support body comprises the following steps: firstly, carrying out rough grinding by using 100-500-mesh sand paper, then carrying out fine grinding by using 1200-2500-mesh sand paper, carrying out ultrasonic cleaning by using acetone, drying, roasting at 200-500 ℃ for 0.5-10 h, and finally carrying out surface modification by using 0.1-10 wt% polydiallyldimethylammonium chloride solution;
step three, steam crystallization: placing the ceramic support body coated with the molecular sieve precursor on the upper end of a reaction kettle with a net-shaped interlayer, then filling deionized water at the bottom, sealing and crystallizing for 1-20 days at 100-180 ℃, then washing until the pH is 7-8, drying at 110-150 ℃ for 1-8 h, and finally roasting and activating at 450-750 ℃ for 1-10 h to obtain the EMT molecular sieve membrane; the deionized water dosage at the bottom of the reaction kettle is determined according to the dried molecular sieve precursor coated on the surface of the ceramic support body, and the specific dosage is as follows: the mass ratio of the deionized water to the molecular sieve precursor is 1:1-1.
2. The method for preparing the EMT molecular sieve membrane according to claim 1, wherein the sol preparation in the first step comprises the following specific steps: respectively weighing an aluminum source, a silicon source, sodium hydroxide, a template agent and deionized water, then fully dissolving the aluminum source into a sodium hydroxide solution under stirring, then adding the silicon source and the template agent into the aluminum solution, finally continuously stirring for 2-8 h, standing and aging for 12-48 h to obtain precursor sol; wherein the adding amount of the aluminum source, the silicon source, the sodium hydroxide, the template agent and the deionized water is according to the Al 2 O 3 : SiO 2 : Na 2 O is a template agent H 2 The molar ratio of O is 1:3-20.
3. The method for preparing the EMT molecular sieve membrane according to claim 1 or 2, wherein the aluminum source comprises one or more of aluminum hydroxide, sodium aluminate, aluminum isopropoxide or bauxite;
the silicon source comprises one or more of solid silica gel, solid sodium silicate, methyl orthosilicate and ethyl orthosilicate;
the template agent is one or a mixture of 15-crown-5 ether, 18-crown-6 ether, polyethylene glycol or polyquaternium-6.
4. The method for preparing the EMT molecular sieve membrane according to claim 1, wherein the temperature of the sol in the first step is 15-40 ℃ and the aging time is 18-36 h.
5. The method according to claim 1, wherein the ceramic support in step two is a tubular porous support with a single-channel or multi-channel structure, and is made of alumina, zirconia or titania;
the average aperture of the ceramic support body is 1-3 mu m, the porosity is 30% -45%, the outer diameter is 12-100 mm, and the inner diameter is 3-50 mm.
6. The method for preparing the EMT molecular sieve membrane according to claim 1 or 5, wherein the method for coating the molecular sieve precursor sol on the surface of the pretreated ceramic support in the second step is placed in an oven at a temperature of between 40 and 85 ℃ and kept for 2 to 24h.
7. The method for preparing an EMT molecular sieve membrane according to claim 1, wherein the steam crystallization temperature in step three is 110-150 ℃ and the time is 3-7 days.
8. The method for preparing the EMT molecular sieve membrane according to claim 1, wherein the thickness of the molecular sieve membrane layer of the prepared EMT molecular sieve membrane is 1-3.0 μm, the particle size of the EMT molecular sieve in the molecular sieve layer is 0.3-1.0 μm, and the average pore size of the molecular sieve is 1.3-2.0 nm.
9. The method for preparing the EMT molecular sieve membrane according to claim 1, wherein the EMT molecular sieve membrane is used for deeply removing polar oxygen-containing compound impurities in a gaseous olefin stream to below 1 ppm.
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