CN107970781B - molecular sieve ceramic membrane material for olefin purification and preparation and application thereof - Google Patents

molecular sieve ceramic membrane material for olefin purification and preparation and application thereof Download PDF

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CN107970781B
CN107970781B CN201711191742.7A CN201711191742A CN107970781B CN 107970781 B CN107970781 B CN 107970781B CN 201711191742 A CN201711191742 A CN 201711191742A CN 107970781 B CN107970781 B CN 107970781B
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molecular sieve
ceramic
ceramic material
solution
ceramic membrane
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CN107970781A (en
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陈伟
周永贤
张春秀
王鹏飞
何秋平
徐华胜
张伏军
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SHANGHAI LUQIANG NEW MATERIALS CO Ltd
Shanghai Research Institute of Chemical Industry SRICI
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Shanghai Research Institute of Chemical Industry SRICI
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5024—Silicates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The invention relates to molecular sieve ceramic membrane materials for olefin purification and preparation and application thereof, wherein the particle size of molecular sieve particles loaded on the surface of a ceramic material in the molecular sieve ceramic membrane materials is 0.1-3 mu m, the thickness of a molecular sieve layer is 3-5 mu m, the molecular sieve ceramic membrane materials are prepared by ceramic material pretreatment, molecular sieve seed crystal precoating and closed crystallization in sequence, and the molecular sieve ceramic membrane materials are used for removing polar oxygen-containing compounds in gaseous olefin flow to below 1 ppm.

Description

molecular sieve ceramic membrane material for olefin purification and preparation and application thereof
Technical Field
The invention belongs to the technical field of inorganic membrane materials, and relates to molecular sieve ceramic membrane materials for olefin purification, and preparation and application thereof.
Background
The polyolefin industry is the backbone of the petrochemical industry and plays an important strategic position in China. As a key premise of olefin polymerization, the polymerization-grade olefin deep purification technology has great influence on the quality and yield of polyolefin products and the future development of downstream plastic industries. With the updating of olefin polymerization catalysts, the purity requirements of the catalysts on raw materials such as ethylene, propylene, butylene and the like are higher and higher. At present, the production technology of olefins mainly comprises: steam cracking, catalytic dehydrogenation, Methanol To Olefin (MTO), Methanol To Propylene (MTP), and the like. The olefin raw material prepared by the traditional cracking method or the novel MTO and MTP processes contains various impurities such as H2O、O2、CO、CO2Methanol, dimethyl ether, propionaldehyde, acetone, carbonyl sulfide, and the like. Especially, the existence of trace methanol, dimethyl ether, propionaldehyde and other polar oxygen-containing compound impurities seriously affects the activity of the polyolefin catalyst, and even can cause the shutdown of the whole device due to catalyst poisoning, thereby causing great economic loss.
At present, when the polar oxygen-containing compounds in olefin flow are deeply purified, widely adopts a process technology method of removing trace amounts of polar oxygen-containing compound impurities such as methanol, dimethyl ether, propionaldehyde and the like in the olefin flow through the adsorption of a granular adsorbent.
Therefore, there is a need to develop new polar oxygen-containing compound purification adsorbents such as methanol, dimethyl ether, and propionaldehyde.
The membrane adsorption and separation technology has the advantages of high precision, low energy consumption, less pollution, easy realization of continuous separation and the like, is widely applied to the industrial fields of chemical industry, food, medicine, environmental protection, metallurgy and the like by , and the molecular sieve ceramic membrane, as novel inorganic membranes developed in more than ten years, not only has the advantages of high temperature resistance, corrosion resistance, high mechanical strength, low mass transfer resistance, large flux and the like, but also has a pore channel structure and structural characteristics which are all adjustable, and is suitable for pervaporation and gas separation.
The U.S. patent publication No. US4699892A synthesizes an A-type molecular sieve layer on the surface of a porous carrier, and shows good permeation and separation performance when the mole contents of methane, ethane and propane are all 33%, and the mole composition of the gas permeated is 73.5% of methane, 26% of ethane and 0.5% of propane, and the U.S. patent publication No. US5464798A is porous α -Al2O3Coating gel on the surface of the ceramic, and crystallizing for 2-3 times in a crystallization solution containing silica gel, NaOH and TPABr to synthesize the Silicalite-1 zeolite molecular sieve ceramic membrane, wherein the molecular sieve ceramic membrane obviously reduces the permeation flux of gas and is 3-14% of the original basal membrane, and N is2Low penetration by 5 times, n-C4H10190 times lower and 1000 times lower. The isobutane can be adsorbed on the membrane obviously, and the separation coefficient of the mixture of the normal isobutane and the isobutane can reach 22. Japanese patent publication No. JP08257301A has a molar composition of H2O/SiO2＝50-120，Na2O/SiO2＝0.5-2，SiO2/Al2O3Under the condition of 5-15, a Y-type molecular sieve membrane is synthesized on a tubular porous support carrier, and when the molecular sieve membrane is used as a pervaporation membrane, the molecular sieve membrane has excellent separation performance on an alcohol-water and alcohol-cyclohexane organic mixed system. Chinese patent application publication No. CN104548956A method for preparing porous α -Al by combining multiple dip-coating of pre-coated crystal seeds with high-temp crystallization2O3The surface of the support is synthesized with NaA molecular sieve membrane with different silicon-aluminum ratios and high separation performance, the membrane has excellent separation performance to isopropanol-water system, European patent with publication number EP674939A2 discloses porous α -Al2O3Method for synthesizing ZSM-5 molecular sieve membrane on ceramic carrier, and ZSM-5/α -Al prepared by method2O3Ceramic membrane for CO in air2Has excellent separation effect, αCO2/N2Can reach 53-56, CO2The penetration rate can reach 1.7 multiplied by 10-7mol/(m2S.Pa.) alternatively, Bejon et Al utilized steam assisted reforming techniques to porous α -Al2O3SAPO-34 molecular sieve membrane is synthesized on the surface of the ceramic carrier, and the ceramic membrane is used for H at room temperature2Has good permeability, and the permeation rate reaches 6.96 multiplied by 10-6mol/(m2S.Pa), for H2/CO2、H2/N2、H2/CH4、H2/C2H6、H2/C3H8、H2/n-C4H10、H2/i-C4H10Have separation coefficients of 1.83, 7.58, 14.80, 18.24, 26.51, 40.15 and 53.02 (see the document Liang Zhou2permeable SAPO-34membranes by steam-assistedconversion seeding[J].International journal of hydrogen energy,2014,39:14949-14954)。
However, the techniques disclosed in the above patents and documents cannot be used for deep purification of polar oxygenates in an olefin stream. Therefore, the synthesis of the molecular sieve ceramic membrane material which is compact, uniform in thickness, free of cracks, free of pores on the surface, high in bonding strength and not easy to fall off and is used for deeply purifying the polar oxygen-containing compounds in the olefin flow is a great technical problem at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide molecular sieve ceramic membrane materials for olefin purification and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme:
A method for preparing a molecular sieve ceramic membrane material for olefin purification, the method comprises the following steps:
1) pretreatment of ceramic materials: roasting the ceramic material at the temperature of 200-800 ℃ for 0.1-12h, then cooling, polishing, cleaning and drying, then placing the ceramic material in a surface modifier solution, soaking at the temperature of 10-150 ℃ for 5min-36h, and then taking out and drying to obtain the pretreated ceramic material;
2) pre-coating molecular sieve crystal seeds: preparing a molecular sieve crystal liquid, coating a molecular sieve crystal seed on the surface of the pretreated ceramic material by using a vacuum filtration process, and then drying to obtain the ceramic material coated with the molecular sieve crystal seed;
3) closed crystallization: and (3) placing the ceramic material coated with the molecular sieve seed crystal in a molecular sieve liquid crystal, aging at 20-80 ℃ for 2-48h, crystallizing at 60-140 ℃ for 4-60h, and drying to obtain the molecular sieve ceramic membrane material.
And coating molecular sieve seed crystals on the ceramic material subjected to surface pretreatment, and then performing a closed crystallization process to obtain the molecular sieve ceramic membrane material for olefin purification.
As a preferable technical scheme, in the step 1), in the roasting process, the roasting temperature is 200-600 ℃, and the roasting time is 1-6 h.
, step 1), grinding with 100 and 2500 meshes of sand paper.
As a preferable technical scheme, the sand paper with 800-1500 meshes is used for grinding.
As a preferable technical scheme, in the step 1), the cleaning method is deionized water ultrasonic cleaning.
, step 1), the surface modifier solution is composed of surface modifier and organic solvent, the surface modifier comprises or more of polydopamine, aminopropyltriethoxysilane, chitosan or hydroxymethyl cellulose, and the organic solvent comprises or two of toluene or TRIS-HCl buffer.
As a preferred technical scheme, the surface modifier is polydopamine or aminopropyltriethoxysilane.
When the surface modifier is polydopamine, the ceramic material pretreatment process comprises the following steps: preparing polydopamine solution according to the ratio of 2-8mL polydopamine (2mg/L)/40-100mL TRIS-HCl, then placing the ceramic material in the polydopamine solution under continuous stirring, soaking at 25-40 ℃ for 10-24h, and drying for later use.
When the surface modifier is aminopropyltriethoxysilane, the ceramic material pretreatment process comprises: preparing a silane solution according to the proportion of 120-460mg aminopropyltriethoxysilane/5-20 mL toluene, then placing the ceramic material in the silane solution, carrying out high-pressure sealing treatment at 80-120 ℃ and 0.01-3Mpa for 30min-3h, drying and cooling for later use.
As a preferable technical scheme, in the step 1), in the soaking treatment process, the soaking temperature is 25-120 ℃, and the soaking time is 30min-24 h.
, in step 1), the ceramic material comprises or more of porous alumina, porous mullite, porous zirconia, porous titania or porous silica, and the ceramic material is in the shape of tube, sheet, layered spiral or ring.
When the ceramic material is porous alumina, α -Al can be selected2O3、γ-Al2O3、δ-Al2O3Or η -Al2O3The average pore diameter of the porous alumina is 0.1-5 μm, and the porosity is 20-80%.
Preferably, the ceramic material is tubular.
, step 2), the molecular sieve crystal liquid is molecular sieve crystal seed liquid sol, which is prepared by mixing aluminum source, silicon source, sodium hydroxide and deionized water according to the ratio of n (Al) n (Si) n (Na) n (H)2Respectively weighing 2:3-25:2-60:300-1320, adding an aluminum source and sodium hydroxide into parts of deionized waterThe preparation method comprises the steps of firstly, stirring to completely dissolve an aluminum source to obtain a solution A, then adding a silicon source into parts of deionized water, stirring to completely dissolve the silicon source to obtain a solution B, then dropwise adding the solution B into the solution A under stirring, stirring at room temperature for 0.5-6h, and then standing and aging for 20-28 h.
And (4) carrying out sol coating on the pretreated ceramic material by using a molecular sieve seed crystal liquid.
The molecular sieve is preferably an LTA type (NaA), FAU type (NaX, NaY, EMT), T type, MFI type or MOR type, and further is preferably a FAU type molecular sieve such as NaX, NaY or EMT.
When the molecular sieve is X type, the mixture ratio of aluminium source, silicon source, sodium hydroxide and deionized water is n (Al), n (Si), n (Na), n (H)2O) 2 (3-7), 6-20, (300-; when the molecular sieve is Y-type, the mixture ratio of aluminium source, silicon source, sodium hydroxide and deionized water is n (Al), n (Si), n (Na), n (H)2O)＝2:(12-30):(10-50):(120-480)。
, the aluminum source comprises or more of aluminum hydroxide, hydrated alumina, sodium aluminate, aluminum sulfate, aluminum isopropoxide, aluminum phosphate or bauxite, and the silicon source comprises or more of solid silica gel, solid sodium silicate, water glass, silica sol, tetraethyl silicate or white carbon black.
As a preferable technical scheme, the aluminum source is aluminum hydroxide, sodium aluminate or aluminum isopropoxide, and the silicon source is solid sodium silicate or water glass.
, when the ceramic material is tubular, the method for coating the molecular sieve seed crystal on the surface of the pretreated ceramic material in the step 2) comprises the steps of uniformly stirring the molecular sieve seed crystal liquid, then blocking the end of the tubular ceramic material, connecting the end of the tubular ceramic material with a vacuum pump, then vertically immersing the tubular ceramic material in the molecular sieve seed crystal liquid, keeping the vacuum degree in the tubular ceramic material at 0.0001-0.01MPa, carrying out suction filtration for 5s-30min, then taking out the tubular ceramic material from the molecular sieve seed crystal liquid, and placing the tubular ceramic material in an oven at 25-65 ℃ for 2-48 h.
As a preferable technical scheme, the vacuum degree in the tubular ceramic material is kept at 0.0001-0.01MPa, and the suction filtration is carried out for 5s-5 min.
As a preferable technical scheme, in the step 3), the aging temperature is 40-70 ℃, the aging time is 4-12h, the crystallization temperature is 80-120 ℃, the crystallization time is 4-24h, and the crystallization reaction times are 1-6.
As a preferred technical proposal, the crystallization process is carried out in a homogeneous reactor, and the rotating speed of a stirrer is 10 to 200r/min during crystallization.
molecular sieve ceramic membrane materials for olefin purification, which are prepared by the method.
, the molecular sieve ceramic membrane material has the ceramic material surface loaded molecular sieve particles with particle size of 0.1-3 μm, the molecular sieve layer with thickness of 3-5 μm, the outer molecular sieve ceramic membrane layer, and continuous and uniform molecular sieve layer, and has high mechanical strength (tensile strength of 120-2And/g), the thickness of the molecular sieve layer is , the molecular sieve layer is compact and uniform, no crack exists in the longitudinal direction and the transverse direction, no pore exists on the surface, the bonding strength is high, and the molecular sieve layer is not easy to fall off.
molecular sieve ceramic membrane material is used for removing polar oxygen-containing compounds in gaseous olefin flow to below 1ppm, the molecular sieve ceramic membrane material has excellent deep purification function, and can remove trace amount of polar oxygen-containing compound impurities such as methanol, dimethyl ether, propionaldehyde, acetone, carbonyl sulfide and the like in gaseous olefin flow such as ethylene or propylene and the like to below 1 ppm.
The application method of the molecular sieve ceramic membrane material comprises the steps of installing the molecular sieve ceramic membrane material in a membrane component, then enabling olefin flow to flow through the molecular sieve ceramic membrane material, and enabling the olefin flow without impurities to penetrate through the membrane and then penetrate through the other side of the membrane.
The activation and regeneration method of the molecular sieve ceramic membrane material comprises the following steps: firstly, blowing the mixture by nitrogen at 60-150 ℃ for 1-8h, and then blowing the mixture by nitrogen at 160-220 ℃ for 0.5-10 h.
The method comprises the steps of soaking a ceramic material which is roasted and polished at a high temperature in a solution containing a surface modifier to obtain a pretreated ceramic material, coating molecular sieve seed crystals on the surface of the pretreated ceramic material by using a sol coating process, and finally performing crystallization reaction under a high-temperature closed condition to obtain a molecular sieve ceramic membrane material, wherein the molecular sieve ceramic membrane material can purify polar oxygen-containing compound impurities, and when the molecular sieve ceramic membrane material adsorbs the polar oxygen-containing compound impurities in olefin flow, the purification depth reaches below 1ppm, so that the molecular sieve ceramic membrane material has small mass transfer resistance, low energy consumption and strong regeneration capacity, can be widely applied to for deeply removing the polar oxygen-containing compound impurities such as methanol, dimethyl ether, propionaldehyde, acetone, carbonyl sulfide and the like in gaseous olefin flow such as ethylene or propylene, and is particularly suitable for deeply purifying the oxygen-containing compound impurities under the conditions of large flow and severe airflow fluctuation, and greatly improves the defect that the molecular sieve layer on the surface of the ceramic tube is easy to fall off in the transportation process.
Research shows that uneven seed coating, overlarge crystal grains and electrostatic repulsion between negatively charged ions in seed liquid and the surface of a ceramic support are main reasons for the failure of synthesizing an ideal molecular sieve ceramic membrane material. The invention selects proper surface modifier to carry out surface modification on the ceramic support in advance, and finally prepares the ideal molecular sieve ceramic membrane material. The molecular sieve ceramic membrane material can replace the granular adsorbent for deeply purifying polar oxygen-containing compounds in the existing olefin flow.
The invention combines surface chemical modification and physical coating process to synthesize compact and compact molecular sieve ceramic membrane material with uniform thickness, no crack, no pore on the surface, high bonding strength and difficult shedding, and the molecular sieve ceramic membrane material has excellent rigidity and mechanical strength, low mass transfer resistance, high heat resistance, deep and efficient removal precision, lower co-adsorption loss of olefins such as ethylene or propylene and the like, has smaller mass transfer resistance, lower energy consumption and longer penetration time than the prior polar oxygen-containing compound impurity purification adsorbent, and solves the defects of large occupied area, large filling volume, high energy consumption and large investment of the prior olefin deep purification process. In addition, the molecular sieve ceramic membrane material also has the advantages of low regeneration temperature and strong regeneration reusability.
Compared with the prior art, the invention has the following characteristics:
1) compared with the prior ceramic tube surface pretreatment technology, the surface modification technology adopted by the invention not only optimizes the roughness of the surface of the ceramic tube, but also forms abundant amino and silicon-oxygen groups on the surface of the ceramic tube after being treated in the specially prepared surface modifier solution, thereby improving the hydrophilicity and electronegativity of the surface of the ceramic tube;
2) the method of the invention combines the surface chemical modification technology and the sol suction filtration technology under vacuum to pre-coat the seed crystal, compared with the existing ceramic tube surface seed crystal coating technology, the existence of the special group of the invention greatly improves the surface property of the ceramic tube, is more beneficial to forming a compact seed crystal layer with uniform thickness in the seed crystal coating stage, and is beneficial to forming a molecular sieve layer with excellent structure and performance;
3) the molecular sieve ceramic membrane material prepared by the invention has high mechanical strength, the molecular sieve on the surface of the ceramic tube is densely and uniformly loaded, the average thickness reaches 3-5 mu m, the molecular sieve particles are smaller, and the average particle size is 0.1-3 mu m; in addition, the obtained molecular sieve layer has no cracks in the longitudinal direction and the transverse direction, no pores exist on the surface, the bonding strength is high, the molecular sieve ceramic membrane is not easy to fall off, and the smaller molecular sieve particles enable the molecular sieve ceramic membrane to have a larger specific surface area, so that the mass transfer and the adsorption of polar oxygen-containing compounds are facilitated;
4) compared with the prior art for deeply purifying polar oxygen-containing compound impurities in olefin flow, the molecular sieve ceramic membrane material prepared by the invention not only meets the requirement of deep purification, but also has small filling volume, low mass transfer resistance, small loss, low regeneration energy consumption when being repeatedly used and high repeated use efficiency;
5) the preparation process of the molecular sieve ceramic membrane material is simple, the investment cost of the previous device is low, and the preparation method is stable and reliable and is easy to realize industrialization.
Drawings
FIG. 1 is an XRD pattern of the ceramic membrane material of molecular sieve prepared in example 1;
FIG. 2 is an SEM image of a molecular sieve ceramic membrane material prepared in example 1, wherein a is a surface SEM image of the molecular sieve ceramic membrane, and b is a cross-sectional SEM image of the molecular sieve ceramic membrane;
FIG. 3 is a graph showing the breakthrough of the molecular sieve ceramic membrane material prepared in example 1 for adsorbing polar oxygen-containing compounds;
FIG. 4 is a graph showing the breakthrough of the molecular sieve ceramic membrane material prepared in example 2 for adsorbing polar oxygen-containing compounds.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
pretreating the ceramic tube by mixing α -Al with average pore diameter of 2 μm and porosity of 55%2O3Placing the ceramic tube in a muffle furnace at 200 ℃ for roasting for 1h, naturally cooling to room temperature, and using 800-mesh sand paper to carry out α -Al treatment2O3Polishing the surface of the ceramic tube smoothly, ultrasonically cleaning the ceramic tube for 2h by using deionized water, drying the ceramic tube in a 120 ℃ oven for 3h, cooling the ceramic tube for later use, and then, polishing the smooth α -Al2O3Soaking the ceramic tube in polydopamine solution: preparing polydopamine solution according to the ratio of 2mL polydopamine (2mg/L)/100mL TRIS-HCl (10mmol/L), then placing the ceramic tube in the polydopamine solution under continuous stirring, soaking at 25 ℃ for 10h, and finally drying for later use.
Preparing molecular sieve seed crystal hydrosol: aluminum hydroxide, sodium silicate, sodium hydroxide and deionized water according to the ratio of n (Al), n (Si), n (Na), n (H)2Mixing the materials in the ratio of O) to 2:3:12:300 at room temperature, and dissolving sodium hydroxide in parts of deionized water, and heating to boilStirring and dissolving aluminum hydroxide in a sodium hydroxide solution to obtain a solution A, adding sodium silicate into parts of deionized water, stirring for 1 hour to completely dissolve the sodium silicate to obtain a solution B, slowly dripping the solution B into the solution A under strong stirring, continuously stirring for 0.5 hour at room temperature, standing and aging for 24 hours at room temperature, and strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal hydrosol, carrying out suction filtration for 5s under the vacuum degree of 0.001MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in a 35 ℃ oven for pretreatment for 48h for later use.
Preparing a molecular sieve ceramic membrane material: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor at 40 ℃ for aging for 12h, heating to 100 ℃, crystallizing at 120r/min for 6h, and repeating the crystallization for 3 times to obtain the 13X molecular sieve ceramic membrane. Washing with deionized water, air drying at room temperature, activating in a 200 deg.C high temperature atmosphere furnace under nitrogen protection for 2h (heating rate of 1 deg.C/min), naturally cooling to room temperature, and testing by XRD and SEM, with the results shown in figures 1 and 2 respectively.
The prepared molecular sieve ceramic membrane material is loaded into a membrane evaluation reactor and purged for 2 hours under the condition of high-purity nitrogen flow at about 100h-1 GHSV. Then, nitrogen gas (about 20X 10) was introduced-6(mol/mol) dimethyl ether DME, methanol METH and propionaldehyde PROP) is continuously fed at the pressure of 0.3MPa at the speed of 20mL/min, and the content of the dimethyl ether, the methanol and the propionaldehyde in the permeate gas passing through the molecular sieve ceramic membrane is detected on line by hydrogen ion gas chromatography. The penetration curve is shown in figure 3.
Example 2:
pretreating the ceramic tube by mixing α -Al with average pore diameter of 0.1 μm and porosity of 20%2O3Placing the ceramic tube in a muffle furnace at 200 ℃ for roasting for 1h, naturally cooling to room temperature, and using 800-mesh sand paper to carry out α -Al treatment2O3The surface of the ceramic tube is polished smoothlyUltrasonic cleaning with deionized water for 2h, drying in oven at 120 deg.C for 3h, cooling, and grinding into smooth α -Al2O3Soaking the ceramic tube in polydopamine solution: preparing polydopamine solution according to the ratio of 2mL polydopamine (2mg/L) to 40mL TRIS-HCl (10mmol/L), then placing the ceramic tube in the polydopamine solution under continuous stirring, soaking at 25 ℃ for 10h, and finally drying for later use.
Preparing molecular sieve seed crystal hydrosol: aluminum hydroxide, sodium silicate, sodium hydroxide and deionized water according to the ratio of n (Al), n (Si), n (Na), n (H)2The method comprises the following steps of dissolving sodium hydroxide in parts of deionized water, stirring and dissolving aluminum hydroxide in a sodium hydroxide solution under the condition of heating and boiling, marking as solution A, adding sodium silicate into parts of deionized water, stirring for 1 hour to completely dissolve the sodium silicate, marking as solution B, slowly dripping the solution B into the solution A under strong stirring, continuously stirring for 0.5 hour at room temperature, standing and aging for 24 hours at room temperature, and strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal sol, carrying out suction filtration for 5s under the vacuum degree of 0.0001MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in an oven at 25 ℃ for pretreatment for 48h for later use.
Preparing a molecular sieve ceramic membrane material: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor at 40 ℃ for aging for 12 hours, heating to 80 ℃, and crystallizing for 48 hours at 10r/min to obtain the 13X molecular sieve ceramic membrane. Washing with deionized water, air drying at room temperature, activating in a 200 deg.C high temperature atmosphere furnace under nitrogen protection for 2h (heating rate of 1 deg.C/min), and naturally cooling to room temperature.
The prepared molecular sieve ceramic membrane material is loaded into a membrane evaluation reactor and purged for 2 hours under the condition of high-purity nitrogen flow at about 100h-1 GHSV. Ethylene gas (about 20) was then introduced×10-6(mol/mol) dimethyl ether DME, methanol METH and propionaldehyde PROP) is continuously fed at the pressure of 0.3MPa at the speed of 20mL/min, and the content of the dimethyl ether, the methanol and the propionaldehyde in the permeate gas passing through the molecular sieve ceramic membrane is detected on line by hydrogen ion gas chromatography. The penetration curve is shown in fig. 4.
Example 3:
pretreating the ceramic tube by mixing α -Al with average pore diameter of 5 μm and porosity of 80%2O3Placing the ceramic tube in a muffle furnace at 200 ℃ for roasting for 1h, naturally cooling to room temperature, and using 1500-mesh sand paper to carry out α -Al treatment2O3Polishing the surface of the ceramic tube smoothly, ultrasonically cleaning the ceramic tube for 2h by using deionized water, drying the ceramic tube in a 120 ℃ oven for 3h, cooling the ceramic tube for later use, and then, polishing the smooth α -Al2O3Soaking the ceramic tube in polydopamine solution: preparing polydopamine solution according to the ratio of 8mL polydopamine (2mg/L) to 100mL TRIS-HCl (10mmol/L), then placing the ceramic tube in the polydopamine solution under continuous stirring, soaking at 25 ℃ for 24h, and finally drying for later use.
Preparing molecular sieve seed crystal hydrosol: aluminum hydroxide, sodium silicate, sodium hydroxide and deionized water according to the ratio of n (Al), n (Si), n (Na), n (H)2The method comprises the following steps of dissolving sodium hydroxide in parts of deionized water, stirring and dissolving aluminum hydroxide in a sodium hydroxide solution under a heating boiling condition, marking as an A solution, adding sodium silicate into parts of deionized water, stirring for 1 hour to completely dissolve the sodium silicate, marking as a B solution, slowly dripping the B solution into the A solution under strong stirring, continuously stirring for 1 hour at room temperature, standing for aging for 24 hours at room temperature, and strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal hydrosol, carrying out suction filtration for 5min under the vacuum degree of 0.01MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in a 65 ℃ oven for pretreatment for 24h for later use.
Preparing a molecular sieve ceramic membrane: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor at 40 ℃ for aging for 12 hours, heating to 110 ℃, and crystallizing for 8 hours at a speed of 50r/min to obtain the Y-type molecular sieve ceramic membrane. Washing with deionized water, air drying at room temperature, activating in a 200 deg.C high temperature atmosphere furnace under nitrogen protection for 2h (heating rate of 1 deg.C/min), and naturally cooling to room temperature.
Example 4:
pretreating the ceramic tube by mixing β -Al with average pore diameter of 3 μm and porosity of 50%2O3The ceramic tube is placed in a muffle furnace at 200 ℃ for roasting for 6h, is naturally cooled to room temperature, and is treated with β -Al by 1500-mesh sand paper2O3Polishing the surface of the ceramic tube smoothly, ultrasonically cleaning the ceramic tube for 2h by using deionized water, drying the ceramic tube in an oven at 100 ℃ for 4h, cooling the ceramic tube for later use, and then, polishing the smooth β -Al2O3Soaking the ceramic tube in polydopamine solution: preparing polydopamine solution according to the ratio of 8mL polydopamine (2mg/L) to 100mL TRIS-HCl (10mmol/L), then placing the ceramic tube in the polydopamine solution under continuous stirring, soaking at 40 ℃ for 24h, and finally drying for later use.
Preparing molecular sieve seed crystal hydrosol: aluminum hydroxide, sodium silicate, sodium hydroxide and deionized water according to the ratio of n (Al), n (Si), n (Na), n (H)2The method comprises the following steps of dissolving sodium hydroxide in parts of deionized water, stirring and dissolving aluminum hydroxide in a sodium hydroxide solution under the condition of heating and boiling, marking as solution A, adding sodium silicate into parts of deionized water, stirring for 1 hour to completely dissolve the sodium silicate, marking as solution B, slowly dripping the solution B into the solution A under strong stirring, continuously stirring for 1 hour at room temperature, standing and aging for 24 hours, and strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal hydrosol, carrying out suction filtration for 30s under the vacuum degree of 0.01MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in an oven at 55 ℃ for pretreatment for 6h for later use.
Preparing a molecular sieve ceramic membrane: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor at 70 ℃ for aging for 6 hours, heating to 120 ℃, and crystallizing for 6 hours at 80r/min to obtain the 13X molecular sieve ceramic membrane. Washing with deionized water, air drying at room temperature, activating in a high temperature atmosphere furnace at 180 deg.C for 3 hr (heating rate of 1 deg.C/min) under the protection of nitrogen, and naturally cooling to room temperature.
Example 5:
pretreatment of the ceramic tube: gamma-Al with an average pore diameter of 3 mu m and a porosity of 50%2O3The ceramic tube is placed in a muffle furnace at 200 ℃ to be roasted for 6h, naturally cooled to room temperature, and the gamma-Al is treated by 1500-mesh abrasive paper2O3Polishing the surface of the ceramic tube smoothly, ultrasonically cleaning the ceramic tube for 2 hours by using deionized water, drying the ceramic tube for 4 hours in a drying oven at the temperature of 100 ℃, and cooling the ceramic tube for later use. gamma-Al to be polished smoothly2O3Soaking the ceramic tube in polydopamine solution: preparing polydopamine solution according to the ratio of 2mL polydopamine (2mg/L) to 100mL TRIS-HCl (10mmol/L), then placing the ceramic tube in the polydopamine solution under continuous stirring, soaking at 40 ℃ for 24h, and finally drying for later use.
Preparing molecular sieve seed crystal hydrosol: aluminum hydroxide, sodium silicate, sodium hydroxide and deionized water according to the ratio of n (Al), n (Si), n (Na), n (H)2The method comprises the following steps of dissolving sodium hydroxide in parts of deionized water, stirring and dissolving aluminum hydroxide in a sodium hydroxide solution under a heating boiling condition, marking as an A solution, adding sodium silicate into parts of deionized water, stirring for 1 hour to completely dissolve the sodium silicate, marking as a B solution, slowly dripping the B solution into the A solution under strong stirring, continuously stirring for 1 hour at room temperature, standing and aging for 24 hours, and strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal hydrosol, carrying out suction filtration for 3min under the vacuum degree of 0.01MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in a 65 ℃ oven for pretreatment for 6h for later use.
Preparing a molecular sieve ceramic membrane: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) placing the closed reaction kettle in a homogeneous reactor at 70 ℃ for aging for 6h, then heating to 120 ℃, crystallizing at 120r/min for 6h, and repeating the crystallization for 3 times to obtain the molecular sieve ceramic membrane material. Washing with deionized water, air drying at room temperature, activating in a high temperature atmosphere furnace at 220 deg.C for 1h (heating rate of 1 deg.C/min) under nitrogen protection, and naturally cooling to room temperature.
Example 6:
pretreating the ceramic tube by mixing η -Al with the average pore diameter of 3 mu m and the porosity of 40%2O3Placing the ceramic tube in a muffle furnace at 600 ℃ for roasting for 4h, naturally cooling to room temperature, and using 1200-mesh sand paper to carry out η -Al treatment2O3Polishing the surface of the ceramic tube smoothly, ultrasonically cleaning the ceramic tube for 2h by using deionized water, drying the ceramic tube in an oven at 100 ℃ for 4h, cooling the ceramic tube for later use, and then, polishing the smooth η -Al2O3Soaking the ceramic tube in polydopamine solution: preparing polydopamine solution according to the ratio of 6mL polydopamine (2mg/L) to 80mL TRIS-HCl (10mmol/L), then placing the ceramic tube in the polydopamine solution under continuous stirring, soaking at 40 ℃ for 24h, and finally drying for later use.
Preparing molecular sieve seed crystal hydrosol: sodium metaaluminate, sodium silicate, sodium hydroxide and deionized water according to the ratio of n (Al), n (Si), n (Na), n (H)2The method comprises the following steps of dissolving sodium hydroxide and sodium metaaluminate in parts of deionized water in sequence, fully stirring for 1 hour to obtain a solution A, adding sodium silicate into parts of deionized water, stirring for 1 hour to completely dissolve the sodium silicate to obtain a solution B, slowly dropping the solution B into the solution A under strong stirring, continuously stirring for 1 hour at room temperature, standing for aging for 24 hours, and strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal hydrosol, carrying out suction filtration for 30s under the vacuum degree of 0.01MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in an oven at 40 ℃ for pretreatment for 10h for later use.
Preparing a molecular sieve ceramic membrane: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor at 70 ℃ for aging for 12h, heating to 120 ℃, crystallizing for 4h at 10r/min, and repeating the crystallization for 6 times to obtain the molecular sieve ceramic membrane material. Washing with deionized water, air drying at room temperature, activating in a high temperature atmosphere furnace at 160 deg.C for 10h (heating rate of 1 deg.C/min) under the protection of nitrogen, and naturally cooling to room temperature.
Example 7:
pretreating the ceramic tube by baking the porous zirconia ceramic tube with average pore diameter of 0.1 μm and porosity of 40% in a muffle furnace at 600 deg.C for 4h, naturally cooling to room temperature, polishing the surface of the zirconia ceramic tube with 1200 mesh abrasive paper, ultrasonically cleaning with deionized water for 2h, drying in an oven at 80 deg.C for 36h, cooling for later use, and drying the polished η -Al2O3Soaking the ceramic tube in polydopamine solution: preparing polydopamine solution according to the ratio of 6mL polydopamine (2mg/L) to 80mL TRIS-HCl (10mmol/L), then placing the ceramic tube in the polydopamine solution under continuous stirring, soaking at 25 ℃ for 24h, and finally drying for later use.
Preparing molecular sieve seed crystal hydrosol: sodium metaaluminate, sodium silicate, sodium hydroxide and deionized water according to the ratio of n (Al), n (Si), n (Na), n (H)2The method comprises the following steps of dissolving sodium metaaluminate and sodium hydroxide in parts of deionized water in sequence, fully stirring for 1 hour to obtain a solution A, adding sodium silicate into parts of deionized water, stirring for 1 hour to completely dissolve the sodium silicate to obtain a solution B, slowly dropping the solution B into the solution A under strong stirring, continuously stirring for 1 hour at room temperature, standing for aging for 24 hours, and strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal hydrosol, carrying out suction filtration for 5s under the vacuum degree of 0.01MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in an oven at 30 ℃ for pretreatment for 10h for later use.
Preparing a molecular sieve ceramic membrane: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor at 50 ℃ for aging for 12 hours, heating to 100 ℃, and crystallizing for 6 hours at 100r/min to obtain the molecular sieve ceramic membrane material. Washing with deionized water, air drying at room temperature, activating in a 200 deg.C high temperature atmosphere furnace under nitrogen protection for 2h (heating rate of 1 deg.C/min), and naturally cooling to room temperature.
Example 8:
pretreating the ceramic tube by mixing porous η -Al with average pore diameter of 4 μm and porosity of 50%2O3Placing the ceramic tube in a muffle furnace at 600 ℃ for roasting for 4h, naturally cooling to room temperature, and using 900-mesh sand paper to carry out η -Al treatment2O3Polishing the surface of a ceramic tube smoothly, ultrasonically cleaning the ceramic tube for 2h by using deionized water, drying the ceramic tube in an oven at the temperature of 80 ℃ for 36h, cooling the ceramic tube for later use, and then, polishing the smooth η -Al2O3Soaking the ceramic tube in a silane solution: preparing a silane solution according to the proportion of 120mg of aminopropyltriethoxysilane/5 mL of toluene, then placing the ceramic tube in the silane solution for high-pressure sealing treatment at 80 ℃ for 3h, drying and cooling for later use.
Preparing molecular sieve seed crystal hydrosol: sodium metaaluminate, sodium silicate, sodium hydroxide and deionized water according to the ratio of n (Al), n (Si), n (Na), n (H)2The method comprises the following steps of dissolving sodium hydroxide and sodium metaaluminate in parts of deionized water in sequence, fully stirring for 1 hour to obtain a solution A, adding solid sodium silicate into parts of deionized water, stirring for 1 hour to completely dissolve the sodium silicate to obtain a solution B, slowly dropwise adding the solution B into the solution A under strong stirring, continuously stirring for 1 hour at room temperature, standing for aging for 24 hours, and strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal hydrosol, carrying out suction filtration for 5s under the vacuum degree of 0.01MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in a 65 ℃ oven for pretreatment for 10h for later use.
Preparing a molecular sieve ceramic membrane: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor at 70 ℃ for aging for 12 hours, heating to 120 ℃, and crystallizing for 4 hours at 120r/min to obtain the molecular sieve ceramic membrane. Washing with deionized water, air drying at room temperature, activating in a 200 deg.C high temperature atmosphere furnace under nitrogen protection for 2h (heating rate of 1 deg.C/min), and naturally cooling to room temperature.
Example 9:
pretreatment of the ceramic tube: placing a porous silicon oxide ceramic tube with the average pore diameter of 2 mu m and the porosity of 60 percent in a 600 ℃ muffle furnace for roasting for 4h, naturally cooling to room temperature, polishing the surface of the silicon oxide ceramic tube by using 1200-mesh sand paper, ultrasonically cleaning for 2h by using deionized water, drying for 4h in a 100 ℃ oven, and cooling for later use. Placing the porous silicon oxide ceramic tube which is polished smoothly into a silane solution for soaking treatment: preparing a silane solution according to the proportion of 460mg aminopropyltriethoxysilane/20 mL toluene, then placing the ceramic tube in the silane solution for high-pressure sealing treatment at 120 ℃ for 30min, drying and cooling for later use.
Preparing molecular sieve seed crystal hydrosol: aluminum isopropoxide, water glass, sodium hydroxide and deionized water according to the proportion of n (Al), n (Si), n (Na), n (H)2Mixing the materials with the proportion of O) 2:12:70:480 at room temperature, wherein the specific method comprises the following steps: sodium hydroxide and aluminum isopropoxide are dissolved in deionized water in sequence and fully stirred for 1 h. Then slowly dripping the water glass solution into the aluminum isopropoxide solution under strong stirring, continuously stirring for 1h at room temperature, standing and aging for 24h, and then strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal hydrosol, carrying out suction filtration for 5s under the vacuum degree of 0.01MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in a 35 ℃ oven for pretreatment for 8h for later use.
Preparing a molecular sieve ceramic membrane: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor at 50 ℃ for aging for 12h, heating to 100 ℃, crystallizing at 80r/min for 6h, and repeating the crystallization for 3 times to obtain the molecular sieve ceramic membrane. Washing with deionized water, air drying at room temperature, activating in a high temperature atmosphere furnace at 220 deg.C for 2 hr (heating rate of 1 deg.C/min) under nitrogen protection, and naturally cooling to room temperature.
Example 10:
pretreatment of the ceramic tube: placing a porous titanium oxide ceramic tube with the average pore diameter of 4 mu m and the porosity of 50 percent in a 600 ℃ muffle furnace for roasting for 4h, naturally cooling to room temperature, polishing the surface of the titanium oxide ceramic tube by using 1200-mesh sand paper, ultrasonically cleaning for 2h by using deionized water, drying for 12h in an 80 ℃ oven, and cooling for later use. Placing the porous silicon oxide ceramic tube which is polished smoothly into a silane solution for soaking treatment: preparing a silane solution according to the proportion of 240mg of aminopropyltriethoxysilane/20 mL of toluene, then placing the ceramic tube in the silane solution for high-pressure sealing treatment at 100 ℃ for 1h, drying and cooling for later use.
Preparing molecular sieve seed crystal hydrosol: aluminum isopropoxide, water glass, sodium hydroxide and deionized water according to the proportion of n (Al), n (Si), n (Na), n (H)2Mixing the materials with the proportion of O) 2:12:70:120 at room temperature, wherein the specific method comprises the following steps: aluminum isopropoxide and sodium hydroxide are dissolved in deionized water in sequence and fully stirred for 1 h. Then slowly dripping water glass into the aluminum isopropoxide solution under strong stirring, continuously stirring for 1h at room temperature, standing and aging for 24h, and then strongly stirring uniformly to obtain the molecular sieve seed crystal hydrosol.
And (3) sol coating, namely plugging the end of the ceramic tube, connecting the end of the ceramic tube with a vacuum pump, vertically immersing the ceramic tube in the molecular sieve seed crystal hydrosol, carrying out suction filtration for 5s under the vacuum degree of 0.01MPa in the tube, slowly taking the ceramic tube out of the sol, plugging the two ends of the ceramic tube by using a plug, and placing the ceramic tube in a 60 ℃ oven for pretreatment for 10h for later use.
Preparing a molecular sieve ceramic membrane: pouring the molecular sieve seed crystal hydrosol into a reaction kettle with a polytetrafluoroethylene lining, and immersing the seed crystal-coated ceramic tube in the molecular sieve seed crystal hydrosol. And (3) sealing the reaction kettle, placing the reaction kettle in a homogeneous reactor at 50 ℃ for aging for 12 hours, heating to 100 ℃, and crystallizing for 6 hours at 80r/min to obtain the molecular sieve ceramic membrane. Washing with deionized water, air drying at room temperature, activating in a high temperature atmosphere furnace at 160 deg.C for 8 hr (heating rate of 1 deg.C/min) under the protection of nitrogen, and naturally cooling to room temperature.
Example 11:
molecular sieve ceramic membrane materials for olefin purification, wherein the particle size of the molecular sieve particles loaded on the surface of the ceramic material is 0.1 μm, and the thickness of the molecular sieve layer is 3 μm.
The preparation method of the molecular sieve ceramic membrane material comprises the following steps:
1) pretreatment of ceramic materials: roasting the ceramic material at 500 ℃ for 6h, cooling, polishing with 1000-mesh sand paper, cleaning, drying, placing the ceramic material in a surface modifier solution, soaking at 80 ℃ for 12h, taking out and drying to obtain a pretreated ceramic material;
2) pre-coating molecular sieve crystal seeds: preparing a molecular sieve crystal liquid, coating a molecular sieve crystal seed on the surface of the pretreated ceramic material by using a vacuum filtration process, and then drying to obtain the ceramic material coated with the molecular sieve crystal seed;
3) closed crystallization: and (3) placing the ceramic material coated with the molecular sieve crystal seeds in a molecular sieve crystal liquid, then aging at 50 ℃ for 24h, then crystallizing at 100 ℃ for 30h, and drying to obtain the molecular sieve ceramic membrane material.
In the step 1), the surface modifier solution consists of a surface modifier and an organic solvent, wherein the surface modifier is polydopamine, and the organic solvent is toluene; the ceramic material is porous zirconia, and the ceramic material is tubular.
In the step 2), the molecular sieve crystal liquid is a molecular sieve crystal seed hydrosol, and the preparation method of the molecular sieve crystal seed hydrosol comprises the following steps:an aluminum source, a silicon source, sodium hydroxide and deionized water according to the formula (n), (Al), (n), (Si), (n), (Na), (N) and (H)2Respectively weighing O) 2:3:60:300, adding an aluminum source and sodium hydroxide into parts of deionized water, stirring to completely dissolve the aluminum source to obtain an A solution, adding a silicon source into parts of deionized water, stirring to completely dissolve the silicon source to obtain a B solution, dropwise adding the B solution into the A solution under stirring, stirring at room temperature for 6 hours, and standing and aging for 20 hours.
The aluminum source comprises aluminum hydroxide and hydrated alumina, and the silicon source comprises solid silica gel and solid sodium silicate.
When the ceramic material is tubular, the method for coating the molecular sieve seed crystal on the surface of the pretreated ceramic material in the step 2) comprises the steps of uniformly stirring the molecular sieve seed crystal liquid, then blocking the end of the tubular ceramic material, connecting the end of the tubular ceramic material with a vacuum pump, vertically immersing the tubular ceramic material in the molecular sieve seed crystal liquid, keeping the vacuum degree in the tubular ceramic material at 0.01MPa, carrying out suction filtration for 5s, then taking out the tubular ceramic material from the molecular sieve seed crystal liquid, and placing the tubular ceramic material in an oven at 65 ℃ for 2 h.
The molecular sieve ceramic membrane material is used for removing polar oxygen-containing compounds in a gaseous olefin flow to below 1 ppm.
Example 12:
molecular sieve ceramic membrane materials for olefin purification, wherein the particle size of the molecular sieve particles loaded on the surface of the ceramic material is 3 μm, and the thickness of the molecular sieve layer is 5 μm.
The preparation method of the molecular sieve ceramic membrane material comprises the following steps:
1) pretreatment of ceramic materials: roasting the ceramic material at 800 ℃ for 0.1h, cooling, polishing with 2500-mesh sand paper, cleaning, drying, placing the ceramic material in a surface modifier solution, soaking at 10 ℃ for 36h, taking out and drying to obtain a pretreated ceramic material;
2) pre-coating molecular sieve crystal seeds: preparing a molecular sieve crystal liquid, coating a molecular sieve crystal seed on the surface of the pretreated ceramic material by using a vacuum filtration process, and then drying to obtain the ceramic material coated with the molecular sieve crystal seed;
3) closed crystallization: and (3) placing the ceramic material coated with the molecular sieve crystal seeds in a molecular sieve crystal liquid, then aging for 48h at 20 ℃, crystallizing for 60h at 60 ℃, and drying to obtain the molecular sieve ceramic membrane material.
In the step 1), the surface modifier solution consists of a surface modifier and an organic solvent, wherein the surface modifier comprises aminopropyltriethoxysilane and chitosan, and the organic solvent is TRIS-HCl buffer solution; the ceramic material is porous mullite, and the ceramic material is tubular.
In the step 2), the molecular sieve crystal liquid is a molecular sieve crystal seed hydrosol, and the preparation method of the molecular sieve crystal seed hydrosol comprises the following steps: an aluminum source, a silicon source, sodium hydroxide and deionized water according to the formula (n), (Al), (n), (Si), (n), (Na), (N) and (H)2Respectively weighing O) 2:25:2:1320, adding an aluminum source and sodium hydroxide into parts of deionized water, stirring to completely dissolve the aluminum source to obtain an A solution, adding a silicon source into parts of deionized water, stirring to completely dissolve the silicon source to obtain a B solution, dropwise adding the B solution into the A solution under stirring, stirring at room temperature for 0.5h, and standing and aging for 28 h.
The aluminum source comprises sodium aluminate, aluminum sulfate and aluminum isopropoxide, and the silicon source comprises water glass, silica sol and tetraethyl silicate.
When the ceramic material is tubular, the method for coating the molecular sieve seed crystal on the surface of the pretreated ceramic material in the step 2) comprises the steps of uniformly stirring the molecular sieve seed crystal liquid, then blocking the end of the tubular ceramic material, connecting the end of the tubular ceramic material with a vacuum pump, vertically immersing the tubular ceramic material in the molecular sieve seed crystal liquid, keeping the vacuum degree in the tubular ceramic material at 0.0001MPa, carrying out suction filtration for 30min, then taking out the tubular ceramic material from the molecular sieve seed crystal liquid, and placing the tubular ceramic material in an oven at 25 ℃ for 48 h.
The molecular sieve ceramic membrane material is used for removing polar oxygen-containing compounds in a gaseous olefin flow to below 1 ppm.
Example 13:
molecular sieve ceramic membrane materials for olefin purification, wherein the particle size of the molecular sieve particles loaded on the surface of the ceramic material is 1 μm, and the thickness of the molecular sieve layer is 4 μm.
The preparation method of the molecular sieve ceramic membrane material comprises the following steps:
1) pretreatment of ceramic materials: roasting the ceramic material at 200 ℃ for 12h, cooling, polishing by 100-mesh abrasive paper, cleaning, drying, placing the ceramic material in a surface modifier solution, soaking at 150 ℃ for 5min, taking out and drying to obtain a pretreated ceramic material;
2) pre-coating molecular sieve crystal seeds: preparing a molecular sieve crystal liquid, coating a molecular sieve crystal seed on the surface of the pretreated ceramic material by using a vacuum filtration process, and then drying to obtain the ceramic material coated with the molecular sieve crystal seed;
3) closed crystallization: and (3) placing the ceramic material coated with the molecular sieve crystal seeds in a molecular sieve crystal liquid, then aging for 2h at 80 ℃, crystallizing for 4h at 140 ℃, and drying to obtain the molecular sieve ceramic membrane material.
In the step 1), the surface modifier solution consists of a surface modifier and an organic solvent, wherein the surface modifier is hydroxymethyl cellulose, and the organic solvent comprises toluene and TRIS-HCl; the ceramic material is porous alumina, and the ceramic material is tubular.
In the step 2), the molecular sieve crystal liquid is a molecular sieve crystal seed hydrosol, and the preparation method of the molecular sieve crystal seed hydrosol comprises the following steps: an aluminum source, a silicon source, sodium hydroxide and deionized water according to the formula (n), (Al), (n), (Si), (n), (Na), (N) and (H)2Respectively weighing O) 2:17:30:800, adding an aluminum source and sodium hydroxide into parts of deionized water, stirring to completely dissolve the aluminum source to obtain an A solution, adding a silicon source into parts of deionized water, stirring to completely dissolve the silicon source to obtain a B solution, dropwise adding the B solution into the A solution under stirring, stirring at room temperature for 2 hours, and standing and aging for 25 hours.
The aluminum source comprises aluminum phosphate and bauxite, and the silicon source is white carbon black.
When the ceramic material is tubular, the method for coating the molecular sieve seed crystal on the surface of the pretreated ceramic material in the step 2) comprises the steps of uniformly stirring the molecular sieve seed crystal liquid, then blocking the end of the tubular ceramic material, connecting the end of the tubular ceramic material with a vacuum pump, vertically immersing the tubular ceramic material in the molecular sieve seed crystal liquid, keeping the vacuum degree in the tubular ceramic material at 0.001MPa, carrying out suction filtration for 10min, then taking out the tubular ceramic material from the molecular sieve seed crystal liquid, and placing the tubular ceramic material in an oven at 45 ℃ for 24 h.
The molecular sieve ceramic membrane material is used for removing polar oxygen-containing compounds in a gaseous olefin flow to below 1 ppm.
Example 14:
in this embodiment, the ceramic material includes porous titanium oxide and porous silicon oxide, and the ceramic material is in a sheet shape, as in embodiment 11.
Example 15:
in this example, the ceramic material is porous titanium oxide, and the ceramic material is a layered spiral, as in example 11.
Example 16:
in this example, the ceramic material is porous zirconia, and the ceramic material is annular, as in example 11.
It will be readily apparent to those skilled in the art that various modifications may be made to the embodiments and the generic principles of described herein may be applied to other embodiments without the use of inventive faculty.

Claims (8)

1, A method for preparing a molecular sieve ceramic membrane material for olefin purification, characterized in that the method comprises the following steps:
1) pretreatment of ceramic materials: roasting the ceramic material at the temperature of 200-800 ℃ for 0.1-12h, then cooling, polishing, cleaning and drying, then placing the ceramic material in a surface modifier solution, soaking at the temperature of 10-150 ℃ for 5min-36h, and then taking out and drying to obtain the pretreated ceramic material;
2) pre-coating molecular sieve crystal seeds: preparing a molecular sieve crystal liquid, coating a molecular sieve crystal seed on the surface of the pretreated ceramic material by using a vacuum filtration process, and then drying to obtain the ceramic material coated with the molecular sieve crystal seed;
3) closed crystallization: placing the ceramic material coated with the molecular sieve crystal seeds in a molecular sieve crystal liquid, then aging at 20-80 ℃ for 2-48h, then crystallizing at 60-140 ℃ for 4-60h, and drying to obtain a molecular sieve ceramic membrane material;
in the step 1), the surface modifier solution consists of a surface modifier and an organic solvent, wherein the surface modifier comprises or more of polydopamine, aminopropyltriethoxysilane, chitosan or hydroxymethyl cellulose, and the organic solvent comprises or two of toluene or TRIS-HCl buffer solution;
in the step 2), the molecular sieve crystal liquid is a molecular sieve crystal seed hydrosol, and the preparation method of the molecular sieve crystal seed hydrosol comprises the following steps: an aluminum source, a silicon source, sodium hydroxide and deionized water according to the formula (n), (Al), (n), (Si), (n), (Na), (N) and (H)2Respectively weighing O) 2:3-25:2-60:300-1320, adding an aluminum source and sodium hydroxide into parts of deionized water, stirring to completely dissolve the aluminum source to obtain an A solution, adding a silicon source into parts of deionized water, stirring to completely dissolve the silicon source to obtain a B solution, dropwise adding the B solution into the A solution under stirring, stirring at room temperature for 0.5-6h, and standing and aging for 20-28 h.
2. The method for preparing molecular sieve ceramic membrane materials for olefin purification according to claim 1, wherein in step 1), the sand paper with 100-2500 meshes is used for grinding.
3. The method for preparing molecular sieve ceramic membrane materials for olefin purification according to claim 1, wherein in step 1), the ceramic materials comprise or more of porous alumina, porous mullite, porous zirconia, porous titania or porous silica, and the ceramic materials are in a tubular shape, a sheet shape, a layered spiral shape or a ring shape.
4. The method of molecular sieve ceramic membrane materials for olefin purification according to claim 1, wherein the aluminum source comprises or more of aluminum hydroxide, hydrated alumina, sodium aluminate, aluminum sulfate, aluminum isopropoxide, aluminum phosphate or bauxite, and the silicon source comprises or more of solid silica gel, solid sodium silicate, water glass, silica sol, tetraethyl silicate or white carbon.
5. The preparation method of molecular sieve ceramic membrane material for olefin purification, according to claim 1, wherein when the ceramic material is tubular, the step 2) of coating molecular sieve seeds on the surface of the pretreated ceramic material comprises stirring the molecular sieve seed liquid uniformly, blocking the end of the tubular ceramic material, connecting the end to a vacuum pump, vertically immersing the tubular ceramic material in the molecular sieve seed liquid, keeping the vacuum degree in the tubular ceramic material at 0.0001-0.01MPa, suction-filtering for 5s-30min, taking out the tubular ceramic material from the molecular sieve seed liquid, and placing the tubular ceramic material in an oven at 25-65 ℃ for 2-48 h.
molecular sieve ceramic membrane material for olefin purification, characterized in that it is prepared by the method according to any of claims 1 to 5, .
7. The molecular sieve ceramic membrane material for olefin purification of claim 6, wherein the molecular sieve particles loaded on the surface of the ceramic material have a particle size of 0.1-3 μm, and the molecular sieve layer has a thickness of 3-5 μm.
Use of the molecular sieve ceramic membrane material of claim 6 for removing polar oxygenates to below 1ppm from a gaseous olefin stream in .
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