CN110898684A - 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 Al2O3:SiO2:Na2O is a template agent H2Weighing an aluminum source, a silicon source, sodium hydroxide and a template agent according to the molar ratio of O to (0.1-10) to (0-1.0) to (20-400) of 1 to (1-50), fully dissolving the aluminum source, the silicon source, the sodium hydroxide and the template agent 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. ceramic support body coated with molecular sieve precursor solAnd (3) placing the membrane 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 due to the advantages of high temperature resistance, corrosion resistance, high mechanical strength, low mass transfer resistance, large flux, uniform and adjustable pore channel 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 an EM for separating C8 aromatic hydrocarbon isomerThe patent provides a preparation method of a porous hollow fiber ceramic membrane by using alumina as a raw material, then a membrane pretreatment agent is used for pretreating the surface of the ceramic membrane, finally a secondary growth method is used for preparing a plurality of layers of EMT molecular sieves on the surface of the ceramic membrane, the prepared EMT molecular sieve membrane has good separation performance of C8 aromatic isomers, but the preparation yield of the membrane in the method can not meet the requirement, the utilization rate of the raw material is low in the preparation process of the EMT molecular sieve membrane layer, Sankhanilay and the like report that a small-particle EMT molecular sieve with 200 nm-1 mu m and uniformly dispersed in water is used as a seed crystal, and then the seed crystal is coated on α -Al modified by cationic polymer poly (diallyl dimethyl ammonium chloride)2O3The EMT molecular sieve membrane with the thickness of 2 mu m is prepared on the surface and finally is hydrothermally crystallized, washed, dried and roasted in the gel with the same composition, but the method has the defects of complex operation, long membrane preparation time and low raw material utilization rate (Sankhanilay Roy Chowndhury) [ Synthesis and construction of EMT-type membranes and the needle performance in-situ filtration experiments)]Journal of membrane science 2008,314: 200-. 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, it is urgently needed to develop a technology for preparing the EMT molecular sieve membrane, which has the advantages of simpler preparation process, shorter membrane preparation time, higher membrane formation rate and raw material utilization rate and more complete membrane structure.
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 Al2O3:SiO2:Na2O is a template agent H2Weighing an aluminum source, a silicon source, sodium hydroxide and a template agent according to the molar ratio of O to (0.1-10) to (0-1.0) to (20-400) of 1 (1-50), fully dissolving the aluminum source, the silicon source, the sodium hydroxide and the template agent in deionized water, continuously stirring for 1-12 h, and then standing and aging at 5-80 ℃ for 12-72 h 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 drying at 25-90 ℃ for 1-48 h 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 the aluminum-based catalystObtaining 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 Al2O3:SiO2:Na2O is a template agent H2The molar ratio of O is preferably 1:3 to 20:1 to 6:0.5 to 0.9:60 to 300.
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 average pore diameter of the ceramic support body is 1-3 μm, the porosity is 30-45%, the outer diameter is 12-100 mm, and the inner diameter is 3-50 mm.
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 blocking one end of the 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 an oven at 40-85 ℃ for 2-24 h.
The pretreatment of the ceramic support body in the second step comprises the following steps: firstly, carrying out coarse polishing by using 100-500-mesh sand paper, then carrying out fine polishing 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, soaking the roasted ceramic support body in 0.1-10 wt% of poly (diallyldimethylammonium chloride) solution for surface modification for 1-10 h. The surface of the ceramic support body is modified by adopting the cationic polymer, so that the roughness of the surface of the ceramic support body is optimized, rich groups are formed on the surface of the modified ceramic support body, the hydrophilicity and the electronegativity of the surface of the ceramic support body 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 on the upper end of a reaction kettle with a mesh 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 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: 60.
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 body to ensure that the surface of the ceramic support body 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 body, 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 dry gel 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 existing EMT molecular sieve membrane, the EMT molecular sieve membrane prepared by the invention has high mechanical strength and strong binding force between the EMT molecular sieve and the ceramic support, the EMT molecular sieve loaded on the surface of the ceramic support 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 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:
pretreating the ceramic support by using single channel α -Al with average pore diameter of 1 μm, porosity of 30%, outer diameter of 12mm and inner diameter of 8mm2O3Cutting the ceramic tube into short tubes of 40mm, polishing and smoothing by using 280-mesh and 1500-mesh abrasive paper in sequence, ultrasonically cleaning for 1h by using acetone and deionized water in sequence, drying for 4h in a drying oven at 110 ℃, roasting for 10h in a muffle furnace at 200 ℃, naturally cooling to room temperature, soaking the ceramic support body in a 1 wt% poly (diallyldimethylammonium chloride) solution for 5min, taking out, washing away excessive poly (diallyldimethylammonium chloride) on the surface by using deionized water, and drying for 2h at 50 ℃.
Sol preparation: according to Al2O3:SiO2:Na2O is a template agent H2Weighing sodium aluminate, silica sol, sodium hydroxide, 15-crown-5 ether and water according to the molar ratio of 1:3:5:0.7: 160. 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 for 36h at 20 ℃ 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 to the pH of 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 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 100ml/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:
pretreating the ceramic support by mixing single channel α -Al with average pore diameter of 3 μm, porosity of 45%, outer diameter of 100mm and inner diameter of 50mm2O3Cutting 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 for 1h by using acetone and deionized water in sequence, drying for 4h in a drying oven at 110 ℃, roasting for 0.5h in a muffle furnace at 500 ℃, naturally cooling to room temperature for later use, and finally, placing in a 0.1 wt% poly (diallyldimethylammonium chloride) solution for surface modification.
Sol preparation: according to Al2O3:SiO2:Na2O is a template agent H2Weighing sodium aluminate, silica sol, sodium hydroxide, 15-crown-5 ether and water according to the molar ratio of 1:5:4:0.9: 260. First, sodium aluminate is dissolved in a sodium hydroxide solution, and then continuouslyRespectively adding the silica sol and 15-crown-5 ether into the aluminum solution under stirring, continuing stirring for 12h, and then standing and aging for 18h 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 10min under the vacuum degree of 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 pretreatment for 2h for later use.
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 1:60), 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 100ml/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:
pretreating the ceramic support by using single channel α -Al with average pore diameter of 3 μm, porosity of 40%, outer diameter of 50mm and inner diameter of 10mm2O3Cutting 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 for 4 hours in an oven at the temperature of 140 ℃, roasting the short tubes for 2 hours in a muffle furnace at the temperature of 600 ℃, naturally cooling the short tubes to room temperature for later use, and finally, placing the short tubes in 10 wt% polydiallyldimethylammonium chloride solution for surface modification.
Sol preparation: according to Al2O3:SiO2:Na2O is a template agent H2Weighing sodium aluminate, silica sol, sodium hydroxide, 18-crown-6 ether and water according to the molar ratio of 1:5:6:0.8: 300. 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 4 hours, and then standing and aging for 24 hours at 30 ℃ 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 10min under the vacuum degree of 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 pretreatment for 2h for later use.
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 1.5 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.
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 extrusion2Cutting the ceramic tube into 50mm short tubes, polishing with 200-mesh and 2000-mesh abrasive paper, and ultrasonically cleaning with acetone and deionized waterWashing for 2h, drying in an oven at 140 ℃ for 4h, finally roasting in a muffle furnace at 300 ℃ for 2h, naturally cooling to room temperature, finally soaking the ceramic support body in a 3 wt% poly (diallyldimethylammonium chloride) solution for 5min, taking out, washing off excessive poly (diallyldimethylammonium chloride) on the surface by deionized water, and drying at 50 ℃ for 2 h.
Sol preparation: according to Al2O3:SiO2:Na2O is a template agent H2Weighing sodium aluminate, silica sol, sodium hydroxide, 18-crown-6 ether and water according to the molar ratio of 1:6:5:0.8: 140. 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: 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 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 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 1.8 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.
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 8mm2Cutting the ceramic tube into short tubes of 40mm, polishing and smoothing the short tubes by using sand paper of 250 meshes and 2500 meshes in sequence, ultrasonically cleaning the short tubes for 2 hours by using acetone and deionized water in sequence, drying the short tubes for 4 hours in a drying oven at the temperature of 140 ℃, roasting the short tubes for 2 hours in a muffle furnace at the temperature of 200 ℃, naturally cooling the short tubes to room temperature, soaking the ceramic support body in 8 wt% polydiallyl dimethyl ammonium chloride solution for 5 minutes, taking out the ceramic support body, washing off redundant polydiallyl dimethyl ammonium chloride on the surface by using deionized water, and drying the ceramic support body for 2 hours at the temperature of 50 ℃.
Sol preparation: according to Al2O3:SiO2:Na2O is a template agent H2Weighing sodium aluminate, silica sol, sodium hydroxide, 18-crown-6 ether and water according to the molar ratio of 1:3:6:0.5: 140. 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 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 a 60 ℃ oven for pretreatment for 3h for later use.
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 1.3 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.
Example 6
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreating the ceramic support by using single channel α -Al with average pore diameter of 2 μm, porosity of 45%, outer diameter of 12mm and inner diameter of 8mm2O3Cutting the ceramic tube into short tubes of 45mm, 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 sequence, drying in an oven of 150 ℃ for 2h, roasting in a muffle furnace of 250 ℃ for 3h, naturally cooling to room temperature for later use, and finally placing in a 5 wt% poly (diallyldimethylammonium chloride) solution for surface modification.
Sol preparation: according to Al2O3:SiO2:Na2O is a template agent H2Weighing sodium aluminate, silica sol, sodium hydroxide, 18-crown-6 ether and water according to the molar ratio of 1:20:6:0.9: 160. 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: 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 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 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 1.8 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.
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.
Sol preparation: according to Al2O3:SiO2:Na2O is a template agent H2Hydrated alumina, water glass, sodium hydroxide, polyquaternium-6 and water are weighed according to the molar ratio of O to be 1:1:0.1:0: 20. 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: 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 5s under the pressure 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 40 ℃ for keeping for 24 hours for later use.
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 20 days at 100 ℃, then washing to pH 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 1.5 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.
Example 8
A preparation method of an EMT molecular sieve membrane comprises the following steps:
pretreating the ceramic support by using single channel α -Al with average pore diameter of 2 μm, porosity of 45%, outer diameter of 12mm and inner diameter of 8mm2O3Cutting the ceramic tube into short tubes of 45mm, 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 sequence, drying in an oven of 150 ℃ for 2h, roasting in a muffle furnace of 250 ℃ for 3h, naturally cooling to room temperature for later use, and finally placing in a 5 wt% poly (diallyldimethylammonium chloride) solution for surface modification.
Sol preparation: according to Al2O3:SiO2:Na2O is a template agent H2Weighing aluminum hydroxide, solid silica gel, sodium hydroxide, polyethylene glycol and water according to the molar ratio of O to the solid silica gel to the water to be mixed, wherein the molar ratio of O to the solid silica gel to the polyethylene glycol to the water is 1:50:10:1.0: 400. 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 two ends of the ceramic tube by using plugs, and placing the ceramic tube in an oven at 85 ℃ for 2 hours for later use.
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 1:60), 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 2 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.
Claims (10)
1. The preparation method of the EMT molecular sieve membrane is characterized by comprising the following steps:
step one, sol preparation: according to Al2O3:SiO2:Na2O is a template agent H2Weighing an aluminum source, a silicon source, sodium hydroxide and a template agent according to the molar ratio of O to (0.1-10) to (0-1.0) to (20-400) of 1 (1-50), fully dissolving the aluminum source, the silicon source, the sodium hydroxide and the template agent in deionized water, continuously stirring for 1-12 h, and then standing and aging at 5-80 ℃ for 12-72 h 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 drying at 25-90 ℃ for 1-48 h 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.
2. The method for preparing an 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 Al2O3:SiO2:Na2O is a template agent H2The molar ratio of O is 1: 3-20: 1-6: 0.5-0.9: 60-300.
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, 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.
4. The preparation method of the EMT molecular sieve membrane of 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 pore diameter 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 an 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 specifically comprises: uniformly stirring the molecular sieve precursor sol, then blocking one end of the 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 an oven at 40-85 ℃ for 2-24 h.
7. The method for preparing an EMT molecular sieve membrane according to claim 1, wherein the pretreatment of the ceramic support in the second step is: firstly, carrying out coarse polishing by using 100-500-mesh sand paper, then carrying out fine polishing 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% of poly (diallyldimethylammonium chloride) solution.
8. The method for preparing an EMT molecular sieve membrane according to claim 1, wherein the steam crystallization process in step three is: placing the ceramic support body coated with the molecular sieve precursor on the upper end of a reaction kettle with a mesh 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 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: 60.
9. 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 3.0 μm, the particle size of the EMT molecular sieve in the molecular sieve layer is 1.0 μm, and the average pore size of the molecular sieve is 1.3-2.0 nm.
10. 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 1ppm, and the removal performance of the EMT molecular sieve membrane is far better than that of the existing gaseous olefin stream purification material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111992051A (en) * | 2020-09-10 | 2020-11-27 | 南京惟新环保装备技术研究院有限公司 | Novel improved orientation ZSM-5 type molecular sieve membrane and preparation method thereof |
| CN114307689A (en) * | 2022-01-17 | 2022-04-12 | 大连理工大学 | Preparation method for synthesizing A-type zeolite membrane by wet gel conversion |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003255046A1 (en) * | 2002-08-16 | 2004-03-03 | Ngk Insulators, Ltd. | Process for producing zeolite molding and process for producing zeolite laminate composite |
| CN101015763A (en) * | 2006-12-30 | 2007-08-15 | 大连理工大学 | Method for expelling trace amount water in methyl chloride by vapor penetration through NaA zeolite molecular sieve film |
| CN107970781A (en) * | 2017-11-24 | 2018-05-01 | 上海绿强新材料有限公司 | A kind of molecular sieve ceramic membrane materials and its preparation and application for alkene purification |
| CN108796500A (en) * | 2018-07-04 | 2018-11-13 | 肇庆市创业帮信息技术有限公司 | A kind of preparation method of metal MFI-type molecular sieve corrosion prevention film |
| CN109499273A (en) * | 2018-11-26 | 2019-03-22 | 上海绿强新材料有限公司 | A kind of EMT molecular screen membrane and its preparation method and application |
-
2019
- 2019-11-22 CN CN201911155610.8A patent/CN110898684B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003255046A1 (en) * | 2002-08-16 | 2004-03-03 | Ngk Insulators, Ltd. | Process for producing zeolite molding and process for producing zeolite laminate composite |
| CN101015763A (en) * | 2006-12-30 | 2007-08-15 | 大连理工大学 | Method for expelling trace amount water in methyl chloride by vapor penetration through NaA zeolite molecular sieve film |
| CN107970781A (en) * | 2017-11-24 | 2018-05-01 | 上海绿强新材料有限公司 | A kind of molecular sieve ceramic membrane materials and its preparation and application for alkene purification |
| CN108796500A (en) * | 2018-07-04 | 2018-11-13 | 肇庆市创业帮信息技术有限公司 | A kind of preparation method of metal MFI-type molecular sieve corrosion prevention film |
| CN109499273A (en) * | 2018-11-26 | 2019-03-22 | 上海绿强新材料有限公司 | A kind of EMT molecular screen membrane and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| MASAHIKO MATSUKATA ET.AL.: "Synthesis of EMT Zeolite by a Steam-Assisted Crystallization Method Using Crown Ether as a Structure-Directing Agent", 《AMERICAN CHEMICAL SOCIETY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111992051A (en) * | 2020-09-10 | 2020-11-27 | 南京惟新环保装备技术研究院有限公司 | Novel improved orientation ZSM-5 type molecular sieve membrane and preparation method thereof |
| CN111992051B (en) * | 2020-09-10 | 2023-09-29 | 南京惟新环保装备技术研究院有限公司 | ZSM-5 type molecular sieve membrane capable of improving orientation and preparation method thereof |
| CN114307689A (en) * | 2022-01-17 | 2022-04-12 | 大连理工大学 | Preparation method for synthesizing A-type zeolite membrane by wet gel conversion |
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