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CN107970781A - A kind of molecular sieve ceramic membrane materials and its preparation and application for alkene purification - Google Patents

A kind of molecular sieve ceramic membrane materials and its preparation and application for alkene purification Download PDF

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Publication number
CN107970781A
CN107970781A CN201711191742.7A CN201711191742A CN107970781A CN 107970781 A CN107970781 A CN 107970781A CN 201711191742 A CN201711191742 A CN 201711191742A CN 107970781 A CN107970781 A CN 107970781A
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molecular sieve
ceramic
ceramic material
ceramic membrane
membrane materials
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CN107970781B (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 LUQIANG NEW MATERIALS CO Ltd
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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

本发明涉及一种用于烯烃净化的分子筛陶瓷膜材料及其制备与应用，分子筛陶瓷膜材料中，陶瓷材料表面负载的分子筛颗粒的粒径为0.1‑3μm，分子筛层的厚度为3‑5μm；制备时，依次经陶瓷材料预处理、分子筛晶种预涂覆、密闭晶化即可；分子筛陶瓷膜材料用于将气态烯烃流中的极性含氧化合物脱除至1ppm以下。与现有技术相比，本发明制备得到的分子筛陶瓷膜材料不仅具备较高的机械强度、较大的比表面积、厚度均一的分子筛层，而且分子筛层无纵向和横向裂纹，表面无气孔，结合强度高且不易脱落；在吸附烯烃流中的极性含氧化合物杂质时，净化深度达到1ppm以下，不仅传质阻力较小，而且能耗较低，再生能力强。

The invention relates to a molecular sieve ceramic membrane material for olefin purification and its preparation and application. In the molecular sieve ceramic membrane material, the particle size of the molecular sieve particles loaded on the surface of the ceramic material is 0.1-3 μm, and the thickness of the molecular sieve layer is 3-5 μm; During the preparation, the ceramic material pretreatment, molecular sieve seed crystal precoating, and closed crystallization can be carried out sequentially; the molecular sieve ceramic membrane material is used to remove the polar oxygen-containing compound in the gaseous olefin flow to below 1ppm. Compared with the prior art, the molecular sieve ceramic membrane material prepared by the present invention not only has a higher mechanical strength, a larger specific surface area, and a molecular sieve layer with uniform thickness, but also has no longitudinal and transverse cracks in the molecular sieve layer and no pores on the surface. High strength and not easy to fall off; when adsorbing polar oxygen-containing compound impurities in olefin streams, the purification depth can reach below 1ppm, not only the mass transfer resistance is small, but also the energy consumption is low, and the regeneration ability is strong.

Description

A kind of molecular sieve ceramic membrane materials and its preparation and application for alkene purification
Technical field
The invention belongs to inorganic material film technical field, be related to a kind of molecular sieve ceramic membrane materials for alkene purification and Its preparation and application.
Background technology
Polyolefin industry is the pillar of petrochemical industry, occupies national important strategic status.Polymer grade olefin deep purifying skill Key precondition of the art as olefinic polyreaction, to the quality and yield of polyolefin products, and the future of downstream plastic industry Development all produces tremendous influence.With the update of olefin polymerization catalysis, catalysts towards ethylene, propylene, butylene etc. The purity requirement of raw material is higher and higher.At present, the production technology of alkene mainly includes：Steam cracking, catalytic pyrolysis, catalysis are de- Hydrogen, methanol-to-olefins (MTO), preparing propylene from methanol (MTP) etc..Either traditional cracking process, or new MTO, MTP work Skill, all contains various impurity, such as H in the olefin feedstock being prepared2O、O2、CO、CO2, methanol, dimethyl ether, propionic aldehyde, acetone, Carbonyl sulfur etc..The especially presence of trace carbinol, dimethyl ether, propionic aldehyde isopolarity oxygenatedchemicals impurity, not only seriously affects The activity of polyolefin catalyst, or even also because of catalyst poisoning whole device can be caused to stop production, cause great economic loss.
At present, during polarity oxygenatedchemicals in deep purifying olefin stream, widely used technology method is logical Cross methanol, dimethyl ether, propionic aldehyde isopolarity oxygenatedchemicals impurity that granular adsorbent absorption removes trace in olefin stream.So And this method is in deep removal polarity oxygenatedchemicals impurity, there is resistance to mass tranfer is big, contact area is small, consume is big etc. Shortcoming, especially to needing huge energy consumption during granular adsorbent regeneration activating, is unfavorable for energy-saving and emission-reduction, and greatly increase Running cost.
Therefore, there is an urgent need to develop a kind of new methanol, dimethyl ether, the purification absorption of propionic aldehyde isopolarity oxygenatedchemicals Agent.
Film adsorbs and isolation technics, since its precision is high, energy consumption is low, pollute less, is easily achieved the advantages that continuous separation, quilt It is widely used in the industrial circles such as chemical industry, food, medicine, environmental protection, metallurgy.Molecular sieve ceramic membrane grows up as nearly more than ten years A kind of Novel inorganic membrane, not only possess the advantages that high temperature resistant, corrosion resistance, high mechanical properties, low mass transfer resistance, big flux, And homogeneous adjustable pore passage structure and architectural characteristic are also equipped with, it is suitably applied infiltration evaporation and gas separation.At present, it is existing Molecular sieve ceramic membrane mainly have the films such as LTA types, FAU types, T-shaped, MFI type, MOR types, its synthetic method mainly has：Situ Hydrothermal Synthetic method, secondary growth method, microwave process for synthesizing and chemical gaseous phase transfer method.Wherein, using most for secondary growth method.
The United States Patent (USP) of Publication No. US4699892A has synthesized A type molecular sieve layer in porous carrier surface, methane, When ethane, propane molar content are 33%, good permeability and separation performance is shown, the gas molar composition penetrated is Methane 73.5%, ethane 26%, propane 0.5%.The United States Patent (USP) of Publication No. US5464798A is in porous α-Al2O3Ceramic watch Gel is coated on face, then crystallization 2-3 times in the crystallization liquid containing silica gel, NaOH and TPABr, synthesizes Silicalite-1 zeolite molecular sieve ceramic membranes, the molecular sieve ceramic membrane significantly reduce the permeation flux of gas, are former base film 3-14%, N2Penetration is 5 times low, n-C4H10Low 190 times, iso-butane is 1000 times low.Iso-butane obvious produce on film is adsorbed, right Just, the separation of iso-butane mixture can reach 22.The Japan Patent of Publication No. JP08257301A is in a mole composition H2O/SiO2=50-120, Na2O/SiO2=0.5-2, SiO2/Al2O3Under conditions of=5-15, on tubular porous support carrier Y-type zeolite membrane is synthesized, when the molecular screen membrane is as infiltrating and vaporizing membrane, to alcohol-water, alcohol-hexamethylene organic mixed system Possesses excellent separating property.Application publication number is that the Chinese invention patent of CN104548956A discloses one kind using repeatedly leaching The method that stain lifting precoating crystal seed is combined with high temperature Crystallization Phases, in porous α-Al2O3Supporting body surface has synthesized different sial The NaA molecular sieve membrane of the high separability energy of ratio, the film possess isopropanol-water system excellent separating property.Publication No. EP674939A2 European patent discloses one kind in porous α-Al2O3The method that ZSM-5 molecular sieve film is synthesized on ceramic monolith, ZSM-5/ α-the Al prepared2O3Ceramic membrane is to the CO in air2Possess excellent separating effect, αCO2/N2Up to 53-56, CO2 Infiltration rate up to 1.7 × 10-7mol/(m2·S·Pa).In addition, Liang Zhou etc. using steam assist conversion technology porous α- Al2O3Ceramic monolith surface has synthesized SAPO-34 molecular screen membranes, and the ceramic membrane is to H at room temperature2Possess good permeance property, Its infiltration rate has reached 6.96 × 10-6mol/(m2SPa), to H2/CO2、H2/N2、H2/CH4、H2/C2H6、H2/C3H8、 H2/n-C4H10、H2/i-C4H10The separation (ginseng that is respectively 1.83,7.58,14.80,18.24,26.51,40.15 and 53.02 See document Liang Zhou.Highly H2permeable SAPO-34membranes by steam-assisted conversion seeding[J].International journal of hydrogen energy,2014,39:14949- 14954)。
However, the depth that technology disclosed in above-mentioned patent and document is not used to polarity oxygenatedchemicals in olefin stream is net Change.Therefore, synthesize closely knit compact, thickness uniformly, flawless, surface pore-free, bond strength is high and not easily to fall off is used for The molecular sieve ceramic membrane materials of polarity oxygenatedchemicals are the huge technical barriers faced at present in deep purifying olefin stream.
The content of the invention
Purified it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind is used for alkene Molecular sieve ceramic membrane materials and its preparation and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of molecular sieve ceramic membrane materials for alkene purification, this method comprise the following steps：
1) ceramic material pre-processes：Ceramic material is roasted into 0.1-12h at 200-800 DEG C, by cooling, is polished, clear Wash, is dry, then ceramic material being placed in surface modifier solution, immersion treatment 5min-36h, Zhi Houqu at 10-150 DEG C Go out and dry, obtain pretreated ceramic material；
2) molecular sieve seed precoating：Molecular sieve seed liquid is prepared, and utilizes and the pottery of technique after the pre-treatment is filtered by vacuum Ceramic material surface coats molecular sieve seed, dries afterwards, obtains the ceramic material coated with molecular sieve seed；
3) closed crystallization：The ceramic material for being coated with molecular sieve seed is placed in molecular sieve seed liquid, afterwards prior to 20- 2-48h is aged at 80 DEG C, then at crystallization 4-60h at 60-140 DEG C, molecular sieve ceramic membrane materials are made after dry.
Coat molecular sieve seed on the ceramic material after surface preparation, after through closed crystallization process, you can The molecular sieve ceramic membrane materials for alkene purification are prepared.
As preferable technical solution, in step 1), in the roasting process, calcination temperature is 200-600 DEG C, roasting Time 1-6h.
Further, in step 1), polished with the sand paper of 100-2500 mesh.
As preferable technical solution, polished with the sand paper of 800-1500 mesh.
As preferable technical solution, in step 1), the cleaning method is that deionized water is cleaned by ultrasonic.
Further, in step 1), the surface modifier solution is made of surface modifier and organic solvent, described Surface modifier include one kind or more in poly-dopamine, aminopropyl triethoxysilane, chitosan or hydroxymethyl cellulose A variety of, the organic solvent includes one or both of toluene or TRIS-HCl buffer solutions.
As preferable technical solution, the surface modifier is poly-dopamine or aminopropyl triethoxysilane.
When surface modifier is poly-dopamine, ceramic material preprocessing process is：According to 2-8mL poly-dopamines (2mg/ L the ratio of)/40-100mL TRIS-HCl prepares poly-dopamine solution, is then with continuous stirring placed in ceramic material poly- more In bar amine aqueous solution, the immersion treatment 10-24h at 25-40 DEG C is spare after dry.
When surface modifier is aminopropyl triethoxysilane, ceramic material preprocessing process is：According to 120-460mg The ratio of aminopropyl triethoxysilane/5-20mL toluene prepares solution of silane, and then ceramic material is placed in solution of silane, High-pressure sealed processing 30min-3h is carried out at 80-120 DEG C, under 0.01-3Mpa, it is spare after dry cooling.
As preferable technical solution, in step 1), during the immersion treatment, soaking temperature is 25-120 DEG C, Soaking time is 30min-24h.
Further, in step 1), the ceramic material include Woelm Alumina, porous mullite, porous zirconia, One or more in porous titanium oxide or porous silica, and the ceramic material in a tubular form, sheet, stratiform it is spiral Or ring-type.Molecular sieve ceramic membrane materials are used as supporter using porous, inorganic ceramic material.
When ceramic material is Woelm Alumina, α-Al can be selected2O3、γ-Al2O3、δ-Al2O3Or η-Al2O3, and it is porous The average pore size of aluminium oxide is 0.1-5 μm, porosity 20-80%.
As preferable technical solution, the ceramic material is in a tubular form.
Further, in step 2), the molecular sieve seed liquid is molecular sieve seed lyosol, the molecular sieve seed liquid The preparation method of colloidal sol is：By silicon source, silicon source, sodium hydroxide, deionized water according to n (Al):n(Si):n(Na):n(H2O)= 2:3-25:2-60:After 300-1320 is weighed respectively, first silicon source and sodium hydroxide are added into a part of deionized water, stirred Silicon source is completely dissolved, obtains solution A；Silicon source is added in another part deionized water again, stirring is completely dissolved silicon source, B solution is obtained, B solution is added drop-wise in solution A under agitation afterwards, and stirs 0.5-6h at room temperature, stands aging afterwards 20-28h.Deionized water is first divided into two parts by molecular sieve seed lyosol before preparation, using as solution A, B The solvent of solution.
Colloidal sol coating is carried out to pretreated ceramic material using molecular sieve seed liquid.
Molecular sieve is preferably LTA types (NaA), FAU types (NaX, NaY, EMT), T-shaped, MFI type or MOR types, further preferably For the FAU type molecular sieves such as NaX, NaY or EMT.
When molecular sieve is X-type, silicon source, silicon source, sodium hydroxide, the proportioning of deionized water are n (Al):n(Si):n(Na): n(H2O)=2:(3-7):(6-20):(300-600)；When molecular sieve is Y types, silicon source, silicon source, sodium hydroxide, deionized water Proportioning be n (Al):n(Si):n(Na):n(H2O)=2:(12-30):(10-50):(120-480).
Further, the silicon source includes aluminium hydroxide, hydrated alumina, sodium aluminate, aluminum sulfate, aluminium isopropoxide, phosphorus One or more in sour aluminium or bauxite, the silicon source include solid silicone, sodium silicate solid, waterglass, Ludox, One or more in tetraethyl orthosilicate or white carbon.
As preferable technical solution, the silicon source is aluminium hydroxide, sodium aluminate or aluminium isopropoxide, and the silicon source is Sodium silicate solid or waterglass.
Further, when the ceramic material in a tubular form when, in step 2), ceramic material surfaces after the pre-treatment apply The method for covering molecular sieve seed is：Molecular sieve seed liquid is stirred evenly, afterwards blocks one end of tubular ceramic material, it is another Tubular ceramic material vertical, is then immersed in molecular sieve seed liquid, keeps in tubular ceramic material by end connection vacuum pump Vacuum 0.0001-0.01MPa, filters 5s-30min, afterwards takes out tubular ceramic material from molecular sieve seed liquid, juxtaposition 2-48h is kept in 25-65 DEG C of baking oven.
As preferable technical solution, the vacuum 0.0001-0.01MPa in tubular ceramic material is kept, filters 5s- 5min。
As preferable technical solution, in step 3), Aging Temperature is 40-70 DEG C, digestion time 4-12h, crystallization temperature Spend for 80-120 DEG C, crystallization time 4-24h, crystallization number is 1-6 times.
As preferable technical solution, the crystallization process carries out in homogeneous reactor, and during crystallization, blender turns Speed is 10-200r/min.
A kind of molecular sieve ceramic membrane materials for alkene purification, the molecular sieve ceramic membrane materials use the method system It is standby to form.
Further, in the molecular sieve ceramic membrane materials, the particle diameter of the sieve particle of ceramic material surfaces load For 0.1-3 μm, the thickness of molecular sieve layer is 3-5 μm.Molecular sieve ceramic membrane is outer layer molecular screen membrane, molecular sieve layer continuous uniform. Molecular sieve ceramic membrane materials not only possess stronger mechanical strength (tensile strength 120-200MPa), larger specific surface area (500-800m2/ g), and molecular sieve layer thickness is homogeneous, packed uniform, the equal flawless of vertical and horizontal, surface pore-free, knot It is high to close intensity, it is not easily to fall off.
A kind of application of molecular sieve ceramic membrane materials, the molecular sieve ceramic membrane materials are used in gaseous olefin stream Polarity oxygenatedchemicals is removed to below 1ppm.Molecular sieve ceramic membrane materials possess excellent deep purifying function, can make ethene Or the methanol of trace, dimethyl ether, propionic aldehyde, acetone, carbonyl sulfur isopolarity oxygenatedchemicals impurity take off in the gaseous olefin stream such as propylene Except to below 1ppm.Molecular sieve ceramic membrane materials are more oxygen-containing than existing polarity in deep purifying polarity oxygenatedchemicals impurity Compound impurities purifying adsorbent possesses the resistance to mass tranfer of smaller, lower energy consumption.
The application method of molecular sieve ceramic membrane materials is：Molecular sieve ceramic membrane materials are installed in membrane module, Ran Hourang Olefin stream flows through molecular sieve ceramic membrane materials, and the olefin stream for being stripped of impurity is penetrated and passed through from the opposite side of film after film.
The activation of molecular sieve ceramic membrane materials and renovation process are：Nitrogen hot blow 1-8h is used at prior to 60-150 DEG C, then Nitrogen hot blow 0.5-10h is used at 160-220 DEG C.
In the present invention, the ceramic material after high-temperature roasting and polishing is soaked in the solution containing surface modifier first Bubble processing, obtains pretreated ceramic material；Then applied using the ceramic material surfaces of colloidal sol coating processes after the pre-treatment Cover molecular sieve seed；Finally, crystallization is carried out under the conditions of high-temperature closed, that is, molecular sieve ceramic membrane materials are prepared, should Molecular sieve ceramic membrane materials can purify polarity oxygenatedchemicals impurity.Molecular sieve ceramic membrane materials polarity in olefin stream is adsorbed During oxygenatedchemicals impurity, purification depth reaches below 1ppm, and not only resistance to mass tranfer is smaller, but also energy consumption is relatively low, power of regeneration By force.The molecular sieve ceramic membrane materials can be widely applied to methanol, diformazan in the gaseous olefin stream such as deep removal ethene or propylene Ether, propionic aldehyde, acetone, carbonyl sulfur isopolarity oxygenatedchemicals impurity, are particularly suitable for that flow is larger, airflow fluctuation is more violent Under the conditions of deep purifying oxycompound impurity, and it is caducous to substantially improve ceramic tube surface molecular screen layers in transportational process Shortcoming.
Research shows, crystal seed coating is uneven, crystal grain is excessive and crystal seed liquid in negatively charged ion and ceramic support Electrostatic repulsion between body surface face is the main reason for leading to not synthesize preferable molecular sieve ceramic membrane materials.Present invention choosing Select suitable surface modifier and surface modification is carried out in advance to ceramic supporting body, preferable molecular sieve ceramic membrane is finally prepared Material.The granular adsorption of deep purifying polarity oxygenatedchemicals in the alternative existing olefin stream of the molecular sieve ceramic membrane materials Agent.
Surface chemical modification is combined by the present invention with physics coating processes, synthesize closely knit compact, thickness uniformly, nothing splits Line and surface pore-free and high, the not easily to fall off molecular sieve ceramic membrane materials of bond strength, the molecular sieve ceramic membrane materials are having Standby excellent rigidity and mechanical strength, low resistance to mass tranfer, while high heat resistance, is also equipped with depth and efficiently removes essence The loss of the alkene eutectoid contents such as degree, relatively low ethene or propylene, possesses than existing polarity oxygenatedchemicals impurity purifying adsorbent The resistance to mass tranfer of smaller, lower energy consumption, longer time of break-through, solve existing alkene advanced purification process floor space and Admission space is big, high energy consumption, big investment the shortcomings that.In addition, the molecular sieve ceramic membrane materials be also equipped with relatively low regeneration temperature, compared with Strong regeneration repeat performance.
Compared with prior art, the invention has the characteristics that：
1) compared with existing ceramic tube surface preparation technology, the process for modifying surface that the present invention uses not only optimizes The roughness of ceramic pipe surface, and in the surface modifier solution by formulated after processing, ceramic pipe surface is formed Abundant amino, silica group, improve the hydrophily and electronegativity of ceramic pipe surface；
2) present invention using surface chemical modification technology with the method that is combined of colloidal sol suction filtration technology under vacuum come pre-coated Crystal seed, compared with existing ceramic pipe surface crystal seed paint-on technique, the presence of specific groups of the present invention substantially improves ceramic tube Surface nature, be more advantageous to forming consolidation and crystal seed layer in uniform thickness in the crystal seed coating stage, help to be formed structure and The molecular sieve layer of function admirable；
3) the molecular sieve ceramic membrane materials that the present invention is prepared, not only high mechanical strength, but also ceramic tube surface molecular Sieve load packed uniform, average thickness reach 3-5 μm, and sieve particle is smaller, and average grain diameter is 0.1-3 μm；In addition, obtain Molecular sieve layer the equal flawless of vertical and horizontal, surface pore-free, bond strength is high, not easily to fall off, and less molecule Sieve particle makes molecular sieve ceramic membrane possess the specific surface area of bigger, is more advantageous to mass transfer and the absorption of polarity oxygenatedchemicals；
4) compared with polarity oxygenatedchemicals impurity technology in existing deep purifying olefin stream, what the present invention was prepared Molecular sieve ceramic membrane materials, have not only reached deep purifying requirement, and admission space is small, resistance to mass tranfer is low, consume is small, and again Regeneration energy consumption when using again is low, reuses efficient；
5) preparation process of molecular sieve ceramic membrane materials is simple, and early period, device input cost was low, reliable and stable, it is easy to accomplish Industrialization.
Brief description of the drawings
Fig. 1 is the XRD spectrum for the molecular sieve ceramic membrane materials being prepared in embodiment 1；
Fig. 2 is the SEM spectrum for the molecular sieve ceramic membrane materials being prepared in embodiment 1, and wherein a is molecular sieve ceramic membrane Surface SEM figure, b be molecular sieve ceramic membrane section SEM scheme；
Fig. 3 is wearing when the molecular sieve ceramic membrane materials being prepared in embodiment 1 are used to adsorb polarity oxygenatedchemicals Saturating curve map；
Fig. 4 is wearing when the molecular sieve ceramic membrane materials being prepared in embodiment 2 are used to adsorb polarity oxygenatedchemicals Saturating curve map.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention Premised on implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to Following embodiments.
Embodiment 1：
Ceramic tube pre-processes：By the α-Al that average pore size is 2 μm, porosity is 55%2O3Ceramic tube is placed in 200 DEG C of Muffles Kiln roasting 1h, naturally cools to room temperature, with 800 mesh sand paper by α-Al2O3Ceramic pipe surface polishes smooth, deionized water ultrasound 2h is cleaned, 3h is dried in 120 DEG C of baking ovens, cooling is spare.α-the Al that will be polished smooth2O3Ceramic tube is placed in poly-dopamine solution Immersion treatment：It is molten that ratio according to 2mL poly-dopamines (2mg/L)/100mL TRIS-HCl (10mmol/L) prepares poly-dopamine Liquid, is then placed in 25 DEG C of immersion treatment 10h, last drying for standby in poly-dopamine solution by ceramic tube with continuous stirring.
The preparation of molecular sieve seed lyosol：By aluminium hydroxide, sodium metasilicate, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)=2:3:12:300 material proportion mixes at room temperature, and specific method is：It is first that sodium hydroxide is molten Solution in a part of deionized water, then under the conditions of ebuillition of heated by aluminium hydroxide stirring and dissolving in sodium hydroxide solution, It is denoted as solution A；Sodium metasilicate is added in another part deionized water again, stirring 1h is completely dissolved sodium metasilicate, and it is molten to be denoted as B Liquid.Then B solution is slowly dropped in solution A under strong stirring, continuously stirs 0.5h at room temperature, be stored at room temperature aging 24h, then strong stirring uniformly can be prepared by molecular sieve seed lyosol.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 5s is filtered under the vacuum of 0.001MPa in pipe, slowly takes out ceramic tube from colloidal sol, is used Plug stoppers both ends, is placed in 35 DEG C of baking ovens and pre-processes 48h, spare.
The preparation of molecular sieve ceramic membrane materials：Molecular sieve seed lyosol is poured into the reaction with teflon lined In kettle, the ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in 40 DEG C of homogeneous reactions 12h is aged in device, then is warming up to 100 DEG C, 120r/min crystallization 6h, repeats crystallization 3 times, 13X molecular sieve ceramic membranes are made.Spend Simultaneously room temperature is dried for ionized water cleaning, is placed under nitrogen protection in 200 DEG C of high-temperature atmosphere furnaces and is activated 2h (heating rate is 1 DEG C/min) Afterwards, cooled to room temperature, afterwards tests it, XRD and SEM test results difference is as shown in Figure 1 and Figure 2.
The molecular sieve ceramic membrane materials being prepared are fitted into film assessing reactor, in the High Purity Nitrogen of about 100h-1GHSV 2h is purged under flow conditions.Then nitrogen gas are made (containing about 20 × 10-6(mol/mol) dimethyl ether DME, methanol METH, propionic aldehyde PROP) with 20mL/min in the pressure continuous feed of 0.3MPa, the infiltration gas through over-molecular sieve ceramic membrane passes through hydrogen ion gas phase The content of chromatography on-line checking wherein dimethyl ether, methanol, propionic aldehyde.Breakthrough curve is as shown in Figure 3.
Embodiment 2：
Ceramic tube pre-processes：By the α-Al that average pore size is 0.1 μm, porosity is 20%2O3Ceramic tube is placed in 200 DEG C of horses Not kiln roasting 1h, naturally cools to room temperature, with 800 mesh sand paper by α-Al2O3Ceramic pipe surface polishes smooth, and deionized water surpasses Sound cleans 2h, and 3h is dried in 120 DEG C of baking ovens, and cooling is spare.α-the Al that will be polished smooth2O3Ceramic tube is placed in poly-dopamine solution Middle immersion treatment：It is molten that ratio according to 2mL poly-dopamines (2mg/L)/40ml TRIS-HCl (10mmol/L) prepares poly-dopamine Liquid, is then placed in 25 DEG C of immersion treatment 10h, last drying for standby in poly-dopamine solution by ceramic tube with continuous stirring.
The preparation of molecular sieve seed lyosol：By aluminium hydroxide, sodium metasilicate, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)=2:3:12:300 material proportion mixes at room temperature, and specific method is：It is first that sodium hydroxide is molten Solution in a part of deionized water, then under the conditions of ebuillition of heated by aluminium hydroxide stirring and dissolving in sodium hydroxide solution, It is denoted as solution A；Sodium metasilicate is added in another part deionized water again, stirring 1h is completely dissolved sodium metasilicate, and it is molten to be denoted as B Liquid.Then B solution is slowly dropped in solution A under strong stirring, continuously stirs 0.5h at room temperature, be stored at room temperature aging 24h, then strong stirring uniformly can be prepared by molecular sieve seed lyosol.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 5s is filtered under the vacuum of 0.0001MPa in pipe, slowly takes out ceramic tube from colloidal sol, Both ends are stoppered with plug, is placed in 25 DEG C of baking ovens and pre-processes 48h, it is spare.
The preparation of molecular sieve ceramic membrane materials：Molecular sieve seed lyosol is poured into the reaction with teflon lined In kettle, the ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in 40 DEG C of homogeneous reactions 12h is aged in device, then is warming up to 80 DEG C, 10r/min crystallization 48h, 13X molecular sieve ceramic membranes are made.Cleaned simultaneously with deionized water Room temperature is dried, and is placed under nitrogen protection in 200 DEG C of high-temperature atmosphere furnaces after activating 2h (heating rate is 1 DEG C/min), natural cooling To room temperature.
The molecular sieve ceramic membrane materials being prepared are fitted into film assessing reactor, in the High Purity Nitrogen of about 100h-1GHSV 2h is purged under flow conditions.Then ethylene gas is made (containing about 20 × 10-6(mol/mol) dimethyl ether DME, methanol METH, propionic aldehyde PROP) with 20mL/min in the pressure continuous feed of 0.3MPa, the infiltration gas through over-molecular sieve ceramic membrane passes through hydrogen ion gas phase The content of chromatography on-line checking wherein dimethyl ether, methanol, propionic aldehyde.Breakthrough curve is as shown in Figure 4.
Embodiment 3：
Ceramic tube pre-processes：By the α-Al that average pore size is 5 μm, porosity is 80%2O3Ceramic tube is placed in 200 DEG C of Muffles Kiln roasting 1h, naturally cools to room temperature, with 1500 mesh sand paper by α-Al2O3Ceramic pipe surface polishes smooth, deionized water ultrasound 2h is cleaned, 3h is dried in 120 DEG C of baking ovens, cooling is spare.α-the Al that will be polished smooth2O3Ceramic tube is placed in poly-dopamine solution Immersion treatment：It is molten that ratio according to 8mL poly-dopamines (2mg/L)/100ml TRIS-HCl (10mmol/L) prepares poly-dopamine Liquid, is then placed in 25 DEG C of immersion treatment 24h, last drying for standby in poly-dopamine solution by ceramic tube with continuous stirring.
The preparation of molecular sieve seed lyosol：By aluminium hydroxide, sodium metasilicate, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)=2:12:50:300 material proportion mixes at room temperature, and specific method is：First by sodium hydroxide Be dissolved in a part of deionized water, then under the conditions of ebuillition of heated by aluminium hydroxide stirring and dissolving in sodium hydroxide solution In, it is denoted as solution A；Sodium metasilicate is added in another part deionized water again, stirring 1h is completely dissolved sodium metasilicate, is denoted as B Solution.Then B solution is slowly dropped in solution A under strong stirring, continuously stirs 1h at room temperature, be stored at room temperature aging 24h, then strong stirring uniformly can be prepared by molecular sieve seed lyosol.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 5min is filtered under the vacuum of 0.01MPa in pipe, slowly takes out ceramic tube from colloidal sol, Both ends are stoppered with plug, is placed in 65 DEG C of baking ovens and pre-processes 24h, it is spare.
Molecular sieve ceramics film preparation：Molecular sieve seed lyosol is poured into the reaction kettle with teflon lined, The ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in old in 40 DEG C of homogeneous reactors Change 12h, then be warming up to 110 DEG C, 50r/min crystallization 8h, Y type molecular sieve ceramic membrane is made.Cleaned with deionized water and room temperature is dried in the air It is dry, it is placed under nitrogen protection in 200 DEG C of high-temperature atmosphere furnaces after activating 2h (heating rate is 1 DEG C/min), cooled to room temperature.
Embodiment 4：
Ceramic tube pre-processes：By the β-Al that average pore size is 3 μm, porosity is 50%2O3Ceramic tube is placed in 200 DEG C of Muffles Kiln roasting 6h, naturally cools to room temperature, with 1500 mesh sand paper by β-Al2O3Ceramic pipe surface polishes smooth, deionized water ultrasound 2h is cleaned, 4h is dried in 100 DEG C of baking ovens, cooling is spare.β-the Al that will be polished smooth2O3Ceramic tube is placed in poly-dopamine solution Immersion treatment：It is molten that ratio according to 8mL poly-dopamines (2mg/L)/100ml TRIS-HCl (10mmol/L) prepares poly-dopamine Liquid, is then placed in 40 DEG C of immersion treatment 24h, last drying for standby in poly-dopamine solution by ceramic tube with continuous stirring.
The preparation of molecular sieve seed lyosol：By aluminium hydroxide, sodium metasilicate, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)==2:4:16:400 material proportion mixes at room temperature, and specific method is：First by sodium hydroxide Be dissolved in a part of deionized water, then under the conditions of ebuillition of heated by aluminium hydroxide stirring and dissolving in sodium hydroxide solution In, it is denoted as solution A；Sodium metasilicate is added in another part deionized water again, stirring 1h is completely dissolved sodium metasilicate, is denoted as B Solution.Then B solution is slowly dropped in solution A under strong stirring, continuously stirs 1h at room temperature, stand aging 24h, then Strong stirring uniformly can be prepared by molecular sieve seed lyosol.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 30s is filtered under the vacuum of 0.01MPa in pipe, slowly takes out ceramic tube from colloidal sol, is used Plug stoppers both ends, is placed in 55 DEG C of baking ovens and pre-processes 6h, spare.
Molecular sieve ceramics film preparation：Molecular sieve seed lyosol is poured into the reaction kettle with teflon lined, The ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in old in 70 DEG C of homogeneous reactors Change 6h, then be warming up to 120 DEG C, 80r/min crystallization 6h, 13X molecular sieve ceramic membranes are made.Cleaned with deionized water and room temperature is dried in the air It is dry, it is placed under nitrogen protection in 180 DEG C of high-temperature atmosphere furnaces after activating 3h (heating rate is 1 DEG C/min), cooled to room temperature.
Embodiment 5：
Ceramic tube pre-processes：By the γ-Al that average pore size is 3 μm, porosity is 50%2O3Ceramic tube is placed in 200 DEG C of Muffles Kiln roasting 6h, naturally cools to room temperature, with 1500 mesh sand paper by γ-Al2O3Ceramic pipe surface polishes smooth, and deionized water surpasses Sound cleans 2h, and 4h is dried in 100 DEG C of baking ovens, and cooling is spare.γ-the Al that will be polished smooth2O3Ceramic tube is placed in poly-dopamine solution Middle immersion treatment：Poly-dopamine is prepared according to the ratio of 2mL poly-dopamines (2mg/L)/100ml TRIS-HCl (10mmol/L) Solution, is then placed in 40 DEG C of immersion treatment 24h, last drying for standby in poly-dopamine solution by ceramic tube with continuous stirring.
The preparation of molecular sieve seed lyosol：By aluminium hydroxide, sodium metasilicate, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)=2:7:60:800 material proportion mixes at room temperature, and specific method is：It is first that sodium hydroxide is molten Solution in a part of deionized water, then under the conditions of ebuillition of heated by aluminium hydroxide stirring and dissolving in sodium hydroxide solution, It is denoted as solution A；Sodium metasilicate is added in another part deionized water again, stirring 1h is completely dissolved sodium metasilicate, and it is molten to be denoted as B Liquid.Then B solution is slowly dropped in solution A under strong stirring, continuously stirs 1h at room temperature, stand aging 24h, then by force Power, which stirs evenly, can be prepared by molecular sieve seed lyosol.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 3min is filtered under the vacuum of 0.01MPa in pipe, slowly takes out ceramic tube from colloidal sol, Both ends are stoppered with plug, is placed in 65 DEG C of baking ovens and pre-processes 6h, it is spare.
Molecular sieve ceramics film preparation：Molecular sieve seed lyosol is poured into the reaction kettle with teflon lined, The ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in old in 70 DEG C of homogeneous reactors Change 6h, then be warming up to 120 DEG C, 120r/min crystallization 6h, repeat crystallization 3 times, that is, molecular sieve ceramic membrane materials are made.Use deionization Simultaneously room temperature is dried for water cleaning, is placed under nitrogen protection in 220 DEG C of high-temperature atmosphere furnaces after activating 1h (heating rate is 1 DEG C/min), Cooled to room temperature.
Embodiment 6：
Ceramic tube pre-processes：Be 3 μm by average pore size, porosity be 40% by η-Al2O3Ceramic tube is placed in 600 DEG C of Muffles Kiln roasting 4h, naturally cools to room temperature, with 1200 mesh sand paper by η-Al2O3Ceramic pipe surface polishes smooth, deionized water ultrasound 2h is cleaned, 4h is dried in 100 DEG C of baking ovens, cooling is spare.η-the Al that will be polished smooth2O3Ceramic tube is placed in poly-dopamine solution Immersion treatment：It is molten that ratio according to 6mL poly-dopamines (2mg/L)/80mL TRIS-HCl (10mmol/L) prepares poly-dopamine Liquid, is then placed in 40 DEG C of immersion treatment 24h, last drying for standby in poly-dopamine solution by ceramic tube with continuous stirring.
The preparation of molecular sieve seed lyosol：By sodium metaaluminate, sodium metasilicate, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)=2:15:40:320 material proportion mixes at room temperature, and specific method is：Successively by hydroxide Sodium and sodium metaaluminate are dissolved in a part of deionized water, are sufficiently stirred 1h, are denoted as solution A；Sodium metasilicate is added to again another In portions of de-ionized water, stirring 1h is completely dissolved sodium metasilicate, is denoted as B solution.Then B solution is slowly dripped under strong stirring It is added in solution A, continuously stirs 1h at room temperature, stand aging 24h, then uniformly to can be prepared by molecular sieve seed liquid molten for strong stirring Glue.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 30s is filtered under the vacuum of 0.01MPa in pipe, slowly takes out ceramic tube from colloidal sol, is used Plug stoppers both ends, is placed in 40 DEG C of baking ovens and pre-processes 10h, spare.
Molecular sieve ceramics film preparation：Molecular sieve seed lyosol is poured into the reaction kettle with teflon lined, The ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in old in 70 DEG C of homogeneous reactors Change 12h, then be warming up to 120 DEG C, 10r/min crystallization 4h, repeat crystallization 6 times, that is, molecular sieve ceramic membrane materials are made.Use deionization Simultaneously room temperature is dried for water cleaning, is placed under nitrogen protection in 160 DEG C of high-temperature atmosphere furnaces after activating 10h (heating rate is 1 DEG C/min), Cooled to room temperature.
Embodiment 7：
Ceramic tube pre-processes：Be 0.1 μm by average pore size, porosity be that 40% porous zirconia ceramic tube is placed in 600 DEG C Muffle kiln roasting 4h, naturally cools to room temperature, is polished smooth zirconia ceramics pipe surface with 1200 mesh sand paper, deionized water It is cleaned by ultrasonic 2h, 36h is dried in 80 DEG C of baking ovens, cooling is spare.η-the Al that will be polished smooth2O3It is molten that ceramic tube is placed in poly-dopamine Immersion treatment in liquid：Poly-dopamine is prepared according to the ratio of 6mL poly-dopamines (2mg/L)/80mL TRIS-HCl (10mmol/L) Solution, is then placed in 25 DEG C of immersion treatment 24h, last drying for standby in poly-dopamine solution by ceramic tube with continuous stirring.
The preparation of molecular sieve seed lyosol：By sodium metaaluminate, sodium metasilicate, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)=2:12:70:480 material proportion mixes at room temperature, and specific method is：Successively by meta-aluminic acid Sodium and sodium hydroxide are dissolved in a part of deionized water, are sufficiently stirred 1h, are denoted as solution A；Sodium metasilicate is added to again another In portions of de-ionized water, stirring 1h is completely dissolved sodium metasilicate, is denoted as B solution.Then B solution is slowly dripped under strong stirring It is added in solution A, continuously stirs 1h at room temperature, stand aging 24h, then uniformly to can be prepared by molecular sieve seed liquid molten for strong stirring Glue.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 5s is filtered under the vacuum of 0.01MPa in pipe, slowly takes out ceramic tube from colloidal sol, is used Plug stoppers both ends, is placed in 30 DEG C of baking ovens and pre-processes 10h, spare.
Molecular sieve ceramics film preparation：Molecular sieve seed lyosol is poured into the reaction kettle with teflon lined, The ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in old in 50 DEG C of homogeneous reactors Change 12h, then be warming up to 100 DEG C, 100r/min crystallization 6h, molecular sieve ceramic membrane materials are made.Simultaneously room temperature is cleaned with deionized water Dry, be placed under nitrogen protection in 200 DEG C of high-temperature atmosphere furnaces after activating 2h (heating rate is 1 DEG C/min), naturally cool to room Temperature.
Embodiment 8：
Ceramic tube pre-processes：Be 4 μm by average pore size, porosity be 50% porous η-Al2O3Ceramic tube is placed in 600 DEG C of horses Not kiln roasting 4h, naturally cools to room temperature, with 900 mesh sand paper by η-Al2O3Ceramic pipe surface polishes smooth, and deionized water surpasses Sound cleans 2h, and 36h is dried in 80 DEG C of baking ovens, and cooling is spare.η-the Al that will be polished smooth2O3Ceramic tube, which is placed in solution of silane, to be soaked Bubble processing：Solution of silane is prepared according to the ratio of 120mg aminopropyl triethoxysilanes/5mL toluene, is then placed in ceramic tube 80 DEG C of high-pressure sealed processing 3h in solution of silane, dry cooling are spare.
The preparation of molecular sieve seed lyosol：By sodium metaaluminate, sodium metasilicate, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)=2:12:70:480 material proportion mixes at room temperature, and specific method is：Successively by hydroxide Sodium and sodium metaaluminate are dissolved in a part of deionized water, are sufficiently stirred 1h, are denoted as solution A；Sodium silicate solid is added to again In another part deionized water, stirring 1h is completely dissolved sodium metasilicate, is denoted as B solution.Then B solution is delayed under strong stirring Slowly it is added drop-wise in solution A, continuously stirs 1h at room temperature, stand aging 24h, then strong stirring uniformly can be prepared by molecular sieve seed Lyosol.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 5s is filtered under the vacuum of 0.01MPa in pipe, slowly takes out ceramic tube from colloidal sol, is used Plug stoppers both ends, is placed in 65 DEG C of baking ovens and pre-processes 10h, spare.
Molecular sieve ceramics film preparation：Molecular sieve seed lyosol is poured into the reaction kettle with teflon lined, The ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in old in 70 DEG C of homogeneous reactors Change 12h, then be warming up to 120 DEG C, 120r/min crystallization 4h, molecular sieve ceramic membrane is made.Cleaned with deionized water and room temperature dried, It is placed under nitrogen protection in 200 DEG C of high-temperature atmosphere furnaces after activating 2h (heating rate is 1 DEG C/min), cooled to room temperature.
Embodiment 9：
Ceramic tube pre-processes：Be 2 μm by average pore size, porosity be that 60% porous silica ceramic tube is placed in 600 DEG C of horses Not kiln roasting 4h, naturally cools to room temperature, is polished smooth silicon oxide ceramics pipe surface with 1200 mesh sand paper, deionized water surpasses Sound cleans 2h, and 4h is dried in 100 DEG C of baking ovens, and cooling is spare.The porous silica ceramic tube polished smooth is placed in solution of silane Middle immersion treatment：Solution of silane is prepared according to the ratio of 460mg aminopropyl triethoxysilanes/20mL toluene, then by ceramics Pipe is placed in 120 DEG C of high-pressure sealed processing 30min in solution of silane, and dry cooling is spare.
The preparation of molecular sieve seed lyosol：By aluminium isopropoxide, waterglass, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)=2:12:70:480 material proportion mixes at room temperature, and specific method is：Successively by hydroxide Sodium and aluminium isopropoxide dissolving in deionized water, are sufficiently stirred 1h.Then water glass solution is slowly added dropwise under strong stirring Into aluminium isopropoxide solution, 1h is continuously stirred at room temperature, stands aging 24h, then strong stirring uniformly can be prepared by molecular sieve crystalline substance Kind lyosol.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 5s is filtered under the vacuum of 0.01MPa in pipe, slowly takes out ceramic tube from colloidal sol, is used Plug stoppers both ends, is placed in 35 DEG C of baking ovens and pre-processes 8h, spare.
Molecular sieve ceramics film preparation：Molecular sieve seed lyosol is poured into the reaction kettle with teflon lined, The ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in old in 50 DEG C of homogeneous reactors Change 12h, then be warming up to 100 DEG C, 80r/min crystallization 6h, repeat crystallization 3 times, molecular sieve ceramic membrane is made.Cleaned with deionized water And room temperature is dried, it is placed under nitrogen protection in 220 DEG C of high-temperature atmosphere furnaces after activating 2h (heating rate is 1 DEG C/min), it is naturally cold But to room temperature.
Embodiment 10：
Ceramic tube pre-processes：Be 4 μm by average pore size, porosity be that 50% porous titanium oxide ceramic tube is placed in 600 DEG C of horses Not kiln roasting 4h, naturally cools to room temperature, is polished smooth titanium oxide ceramics pipe surface with 1200 mesh sand paper, deionized water surpasses Sound cleans 2h, and 12h is dried in 80 DEG C of baking ovens, and cooling is spare.The porous silica ceramic tube polished smooth is placed in solution of silane Middle immersion treatment：Solution of silane is prepared according to the ratio of 240mg aminopropyl triethoxysilanes/20mL toluene, then by ceramics Pipe is placed in 100 DEG C of high-pressure sealed processing 1h in solution of silane, and dry cooling is spare.
The preparation of molecular sieve seed lyosol：By aluminium isopropoxide, waterglass, sodium hydroxide, deionized water according to n (Al):n (Si):n(Na):n(H2O)=2:12:70:120 material proportion mixes at room temperature, and specific method is：Successively by isopropanol Aluminium and sodium hydroxide dissolving in deionized water, are sufficiently stirred 1h.Then waterglass is slowly dropped under strong stirring different In propyl alcohol aluminum solutions, 1h is continuously stirred at room temperature, stands aging 24h, then strong stirring uniformly can be prepared by molecular sieve seed liquid Colloidal sol.
Colloidal sol coats：Ceramic tube one end is blocked, ceramic tube, is then vertically immersed in above-mentioned by other end connection vacuum pump In molecular sieve seed lyosol, 5s is filtered under the vacuum of 0.01MPa in pipe, slowly takes out ceramic tube from colloidal sol, is used Plug stoppers both ends, is placed in 60 DEG C of baking ovens and pre-processes 10h, spare.
Molecular sieve ceramics film preparation：Molecular sieve seed lyosol is poured into the reaction kettle with teflon lined, The ceramic tube for coating crystal seed is immersed in molecular sieve seed lyosol.Closed reactor is placed in old in 50 DEG C of homogeneous reactors Change 12h, then be warming up to 100 DEG C, 80r/min crystallization 6h, molecular sieve ceramic membrane is made.Cleaned with deionized water and room temperature dried, It is placed under nitrogen protection in 160 DEG C of high-temperature atmosphere furnaces after activating 8h (heating rate is 1 DEG C/min), cooled to room temperature.
Embodiment 11：
A kind of molecular sieve ceramic membrane materials for alkene purification, in the molecular sieve ceramic membrane materials, ceramic material surfaces The particle diameter of the sieve particle of load is 0.1 μm, and the thickness of molecular sieve layer is 3 μm.
The preparation method of molecular sieve ceramic membrane materials comprises the following steps：
1) ceramic material pre-processes：Ceramic material is roasted into 6h at 500 DEG C, polishes by cooling, 1000 mesh sand paper, is clear Wash, be dry, then ceramic material being placed in surface modifier solution, the immersion treatment 12h at 80 DEG C, being taken out afterwards and dry, Obtain pretreated ceramic material；
2) molecular sieve seed precoating：Molecular sieve seed liquid is prepared, and utilizes and the pottery of technique after the pre-treatment is filtered by vacuum Ceramic material surface coats molecular sieve seed, dries afterwards, obtains the ceramic material coated with molecular sieve seed；
3) closed crystallization：The ceramic material for being coated with molecular sieve seed is placed in molecular sieve seed liquid, afterwards prior to 50 24h is aged at DEG C, the crystallization 30h at 100 DEG C, molecular sieve ceramic membrane materials are made after dry.
In step 1), surface modifier solution is made of surface modifier and organic solvent, and surface modifier is poly- DOPA Amine, organic solvent are toluene；Ceramic material is porous zirconia, and ceramic material is in a tubular form.
In step 2), molecular sieve seed liquid is molecular sieve seed lyosol, the preparation method of the molecular sieve seed lyosol For：By silicon source, silicon source, sodium hydroxide, deionized water according to n (Al):n(Si):n(Na):n(H2O)=2:3:60:300 difference After weighing, first silicon source and sodium hydroxide are added into a part of deionized water, stirring is completely dissolved silicon source, obtains solution A； Silicon source is added in another part deionized water again, stirring is completely dissolved silicon source, B solution is obtained, afterwards under agitation by B Solution is added drop-wise in solution A, and stirs 6h at room temperature, stands aging 20h afterwards.
Silicon source includes aluminium hydroxide and hydrated alumina, and silicon source includes solid silicone and sodium silicate solid.
When ceramic material in a tubular form when, in step 2), ceramic material surfaces coating molecular sieve seed after the pre-treatment Method is：Molecular sieve seed liquid is stirred evenly, afterwards blocks one end of tubular ceramic material, other end connection vacuum pump, Then tubular ceramic material vertical is immersed in molecular sieve seed liquid, keeps the vacuum 0.01MPa in tubular ceramic material, 5s is filtered, tubular ceramic material is taken out from molecular sieve seed liquid afterwards, is placed in keeping 2h in 65 DEG C of baking ovens.
The molecular sieve ceramic membrane materials are used to the polarity oxygenatedchemicals in gaseous olefin stream being removed to below 1ppm.
Embodiment 12：
A kind of molecular sieve ceramic membrane materials for alkene purification, in the molecular sieve ceramic membrane materials, ceramic material surfaces The particle diameter of the sieve particle of load is 3 μm, and the thickness of molecular sieve layer is 5 μm.
The preparation method of molecular sieve ceramic membrane materials comprises the following steps：
1) ceramic material pre-processes：Ceramic material is roasted into 0.1h at 800 DEG C, polish by cooling, 2500 mesh sand paper, Cleaning, drying, then ceramic material is placed in surface modifier solution, immersion treatment 36h, takes out and does afterwards at 10 DEG C It is dry, obtain pretreated ceramic material；
2) molecular sieve seed precoating：Molecular sieve seed liquid is prepared, and utilizes and the pottery of technique after the pre-treatment is filtered by vacuum Ceramic material surface coats molecular sieve seed, dries afterwards, obtains the ceramic material coated with molecular sieve seed；
3) closed crystallization：The ceramic material for being coated with molecular sieve seed is placed in molecular sieve seed liquid, afterwards prior to 20 48h is aged at DEG C, the crystallization 60h at 60 DEG C, molecular sieve ceramic membrane materials are made after dry.
In step 1), surface modifier solution is made of surface modifier and organic solvent, and surface modifier includes ammonia third Ethyl triethoxy silicane alkane and chitosan, organic solvent bag are TRIS-HCl buffer solutions；Ceramic material is porous mullite, and is made pottery Ceramic material is in a tubular form.
In step 2), molecular sieve seed liquid is molecular sieve seed lyosol, the preparation method of the molecular sieve seed lyosol For：By silicon source, silicon source, sodium hydroxide, deionized water according to n (Al):n(Si):n(Na):n(H2O)=2:25:2:1320 difference After weighing, first silicon source and sodium hydroxide are added into a part of deionized water, stirring is completely dissolved silicon source, obtains solution A； Silicon source is added in another part deionized water again, stirring is completely dissolved silicon source, B solution is obtained, afterwards under agitation by B Solution is added drop-wise in solution A, and stirs 0.5h at room temperature, stands aging 28h afterwards.
Silicon source includes sodium aluminate, aluminum sulfate and aluminium isopropoxide, and silicon source includes waterglass, Ludox and tetraethyl orthosilicate.
When ceramic material in a tubular form when, in step 2), ceramic material surfaces coating molecular sieve seed after the pre-treatment Method is：Molecular sieve seed liquid is stirred evenly, afterwards blocks one end of tubular ceramic material, other end connection vacuum pump, Then tubular ceramic material vertical is immersed in molecular sieve seed liquid, keeps the vacuum in tubular ceramic material 0.0001MPa, filters 30min, tubular ceramic material is taken out from molecular sieve seed liquid afterwards, is placed in protecting in 25 DEG C of baking ovens Hold 48h.
The molecular sieve ceramic membrane materials are used to the polarity oxygenatedchemicals in gaseous olefin stream being removed to below 1ppm.
Embodiment 13：
A kind of molecular sieve ceramic membrane materials for alkene purification, in the molecular sieve ceramic membrane materials, ceramic material surfaces The particle diameter of the sieve particle of load is 1 μm, and the thickness of molecular sieve layer is 4 μm.
The preparation method of molecular sieve ceramic membrane materials comprises the following steps：
1) ceramic material pre-processes：Ceramic material is roasted into 12h at 200 DEG C, polishes by cooling, 100 mesh sand paper, is clear Wash, is dry, then ceramic material is placed in surface modifier solution, immersion treatment 5min, takes out and do afterwards at 150 DEG C It is dry, obtain pretreated ceramic material；
2) molecular sieve seed precoating：Molecular sieve seed liquid is prepared, and utilizes and the pottery of technique after the pre-treatment is filtered by vacuum Ceramic material surface coats molecular sieve seed, dries afterwards, obtains the ceramic material coated with molecular sieve seed；
3) closed crystallization：The ceramic material for being coated with molecular sieve seed is placed in molecular sieve seed liquid, afterwards prior to 80 2h is aged at DEG C, the crystallization 4h at 140 DEG C, molecular sieve ceramic membrane materials are made after dry.
In step 1), surface modifier solution is made of surface modifier and organic solvent, and surface modifier is methylol Cellulose, organic solvent include toluene and TRIS-HCl；Ceramic material is Woelm Alumina, and ceramic material is in a tubular form.
In step 2), molecular sieve seed liquid is molecular sieve seed lyosol, the preparation method of the molecular sieve seed lyosol For：By silicon source, silicon source, sodium hydroxide, deionized water according to n (Al):n(Si):n(Na):n(H2O)=2:17:30:800 difference After weighing, first silicon source and sodium hydroxide are added into a part of deionized water, stirring is completely dissolved silicon source, obtains solution A； Silicon source is added in another part deionized water again, stirring is completely dissolved silicon source, B solution is obtained, afterwards under agitation by B Solution is added drop-wise in solution A, and stirs 2h at room temperature, stands aging 25h afterwards.
Silicon source includes aluminum phosphate and bauxite, and silicon source is white carbon.
When ceramic material in a tubular form when, in step 2), ceramic material surfaces coating molecular sieve seed after the pre-treatment Method is：Molecular sieve seed liquid is stirred evenly, afterwards blocks one end of tubular ceramic material, other end connection vacuum pump, Then tubular ceramic material vertical is immersed in molecular sieve seed liquid, keeps the vacuum in tubular ceramic material 0.001MPa, filters 10min, tubular ceramic material is taken out from molecular sieve seed liquid afterwards, is placed in protecting in 45 DEG C of baking ovens Hold 24h.
The molecular sieve ceramic membrane materials are used to the polarity oxygenatedchemicals in gaseous olefin stream being removed to below 1ppm.
Embodiment 14：
In the present embodiment, ceramic material includes porous titanium oxide and porous silica, and ceramic material is in the form of sheets, remaining With embodiment 11.
Embodiment 15：
In the present embodiment, ceramic material is porous titanium oxide, and ceramic material is spiral in stratiform, remaining same embodiment 11。
Embodiment 16：
In the present embodiment, ceramic material is porous zirconia, and ceramic material is annular in shape, remaining is the same as embodiment 11.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention. Person skilled in the art obviously easily can make these embodiments various modifications, and described herein general Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability Field technique personnel disclose according to the present invention, do not depart from improvement that scope made and modification all should be the present invention's Within protection domain.

Claims (10)

1. the preparation method of a kind of molecular sieve ceramic membrane materials for alkene purification, it is characterised in that this method includes following Step：
1) ceramic material pre-processes：Ceramic material is roasted into 0.1-12h at 200-800 DEG C, by cooling, polishing, is cleaned, dry It is dry, then ceramic material is placed in surface modifier solution, immersion treatment 5min-36h, takes out and does afterwards at 10-150 DEG C It is dry, obtain pretreated ceramic material；
2) molecular sieve seed precoating：Molecular sieve seed liquid is prepared, and utilizes and the ceramic material of technique after the pre-treatment is filtered by vacuum Expect surface coating molecular sieve seed, dry afterwards, obtain the ceramic material coated with molecular sieve seed；
3) closed crystallization：The ceramic material for being coated with molecular sieve seed is placed in molecular sieve seed liquid, afterwards prior to 20-80 DEG C Lower ageing 2-48h, then at crystallization 4-60h at 60-140 DEG C, molecular sieve ceramic membrane materials are made after dry.
2. a kind of preparation method of molecular sieve ceramic membrane materials for alkene purification according to claim 1, its feature It is, in step 1), is polished with the sand paper of 100-2500 mesh.
3. a kind of preparation method of molecular sieve ceramic membrane materials for alkene purification according to claim 1, its feature It is, in step 1), the surface modifier solution is made of surface modifier and organic solvent, the surface modifier Including the one or more in poly-dopamine, aminopropyl triethoxysilane, chitosan or hydroxymethyl cellulose, described has Solvent includes one or both of toluene or TRIS-HCl buffer solutions.
4. a kind of preparation method of molecular sieve ceramic membrane materials for alkene purification according to claim 1, its feature Be, in step 1), the ceramic material include Woelm Alumina, porous mullite, porous zirconia, porous titanium oxide or One or more in porous silica, and the ceramic material in a tubular form, sheet, stratiform be spiral or ring-type.
5. a kind of preparation method of molecular sieve ceramic membrane materials for alkene purification according to claim 1, its feature It is, in step 2), the molecular sieve seed liquid is molecular sieve seed lyosol, the preparation side of the molecular sieve seed lyosol Method is：By silicon source, silicon source, sodium hydroxide, deionized water according to n (Al):n(Si):n(Na):n(H2O)=2:3-25:2-60: After 300-1320 is weighed respectively, first silicon source and sodium hydroxide are added into a part of deionized water, stirring makes silicon source completely molten Solution, obtains solution A；Silicon source is added in another part deionized water again, stirring is completely dissolved silicon source, obtains B solution, it B solution is added drop-wise in solution A under agitation afterwards, and stirs 0.5-6h at room temperature, stands aging 20-28h afterwards.
6. a kind of preparation method of molecular sieve ceramic membrane materials for alkene purification according to claim 5, its feature It is, the silicon source includes aluminium hydroxide, hydrated alumina, sodium aluminate, aluminum sulfate, aluminium isopropoxide, aluminum phosphate or bauxite In one or more, the silicon source include solid silicone, sodium silicate solid, waterglass, Ludox, tetraethyl orthosilicate or One or more in white carbon.
7. a kind of preparation method of molecular sieve ceramic membrane materials for alkene purification according to claim 1, its feature Be, when the ceramic material in a tubular form when, in step 2), ceramic material surfaces coating molecular sieve seed after the pre-treatment Method be：Molecular sieve seed liquid is stirred evenly, afterwards blocks one end of tubular ceramic material, other end connection vacuum Tubular ceramic material vertical, is then immersed in molecular sieve seed liquid by pump, keeps the vacuum in tubular ceramic material 0.0001-0.01MPa, filters 5s-30min, tubular ceramic material is taken out from molecular sieve seed liquid afterwards, is placed in 25- 2-48h is kept in 65 DEG C of baking ovens.
8. a kind of molecular sieve ceramic membrane materials for alkene purification, it is characterised in that the molecular sieve ceramic membrane materials are using such as Claim 1 to 7 any one of them method is prepared.
9. a kind of molecular sieve ceramic membrane materials for alkene purification according to claim 8, it is characterised in that described In molecular sieve ceramic membrane materials, the particle diameter of the sieve particle of ceramic material surfaces load is 0.1-3 μm, the thickness of molecular sieve layer For 3-5 μm.
A kind of 10. application of molecular sieve ceramic membrane materials as claimed in claim 8, it is characterised in that the molecular sieve pottery Porcelain membrane material is used to the polarity oxygenatedchemicals in gaseous olefin stream being removed to below 1ppm.
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