CN109499273A - A kind of EMT molecular screen membrane and its preparation method and application - Google Patents
A kind of EMT molecular screen membrane and its preparation method and application Download PDFInfo
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention relates to a kind of EMT molecular screen membrane and its preparation method and application, EMT molecular sieve ceramic membrane materials are to be made of ceramic supporting body with the EMT sieve particle for being supported on surface, and the partial size of EMT molecular sieve is 1.5~2 μm, and molecular sieve thicknesses of layers is 3~4 μm；The preparation method is as follows: ceramic supporting body is passed through cationic polymer surface preparation, then ceramic supporting body precoating surfaces molecular sieve seed after modification, is finally placed in closed crystallization in Synthesis liquid.Inventive film high yield rate, the binding force between the EMT molecular sieve ceramic membrane materials high mechanical strength, molecular sieve and the ceramic supporting body that are prepared is strong and not easily to fall off, and pore-size distribution is narrow, thicknesses of layers is uniform, and flawless, and continuity is good；The CO in being applied to natural gas2/CH4When adsorbing separation, has higher CO2Adsorption capacity and αCO2/CH4Separation, lesser resistance to mass tranfer, lower energy consumption and stronger power of regeneration, makes it in CO2/CH4Continuous operation can be achieved in adsorbing separation.
Description
Technical field
The invention belongs to comprehensive utilization of energy fields, are related to a kind of technology of preparing of inorganic material film, are in particular to used for
CO2/CH4Isolated EMT molecular sieve ceramic membrane preparation and application.
Background technique
Natural gas has been widely used for as a kind of important the high-efficiency cleaning energy and industrial chemicals by favor
In industry and daily life.The main component of natural gas is CH4, in addition to this also contain CO2Such sour gas.CO2Deposit
In the product quality for not only having seriously affected natural gas, but also the condensed water and acid generated during natural gas processing, can also
Serious corrosiveness is caused to equipment and pipeline.Therefore, there is an urgent need to CO is isolated from natural gas2, to improve CH4It is pure
Degree is to obtain higher-quality gas product.In addition, the CO separated2As a kind of " potential carbon resource ", Ke Yiwei
Subsequent CO2Industrial expansion provides more fully raw material sources.
Tradition removing CO2Commercial run mainly have: solvent absorption, cryogenic separation method, cryogenic condensation separation, absorption point
From method etc..In contrast, the features such as membrane separation process is due to its high efficiency, highly selective, inexpensive and easy continuous operation and it is standby
Favored.More documents and patent report using membrane material remove separation CO2And CH4, including polymeric membrane and molecular screen membrane.
The Chinese invention patent of 103608094 B of patent CN discloses a kind of high CO2/CH4The metal-of separating property is organic
Skeleton structure membrane material and preparation method thereof, the membrane material are with α-Al2O3For carrier, using in situ synthesis in α-Al2O3Table
Load C AU-1 film layer on face, then again by α-Al2O3/ CAU-1 ceramic membrane is placed in the toluene of 3- isocyanide propyl-triethoxysilicane
In solution, inert gas shielding processing is finally washed, compact closely knit metal-organic framework structural membrane is prepared in drying；It should
Membrane material is for separating CO2With CH4When Deng other macromolecular gases, compared with unmodified CAU-1 film, CO2The selection of molecule is saturating
The rate of mistake greatly improves, but the patent preparation condition is harsh, and preparation cost is higher, is unfavorable for industrialized production.Praxair Technology, Inc
102892485 B of patent of invention CN disclose a kind of high osmosis polyimide film for air separation, the membrane material
Be with 3,3 ', 4,4 '-diphenylsulfone acid's dianhydrides (DSDA) and pyromellitic acid dianhydride (PMDA) and 3,3 ', 5,5 '-tetramethyl -4,
Poly- (3,3 ', 4,4 '-diphenylsulfone acid's dianhydrides-pyromellitic acid that the condensation reaction of 4 '-methylene dianiline (MDA)s (TMMDA) obtains
Dianhydride -3,3 ', 5,5 '-tetramethyls -4,4 '-methylene dianiline (MDA)) it is that the doughnut that raw material is prepared through spinning is asymmetric
Film；It is 791kPa in pressure, temperature is at 50 DEG C, and the Polyimide Hollow Fiber is in CO2/CH4Have when separation and is higher than
The CO of 1000GPU2Permeability and CO higher than 202/CH4Single gas-selectively is a kind of organic film prepared by the patent, system
The monomer material of standby film is complicated, and at high cost, non-refractory limits its industrial applications.201710243112.3 disclosure of patent
A kind of method preparing SAPO-34 molecular screen membrane, uses cheap diethylamine (DEA) for template, uses diauxic growth
Method synthesizes one layer of fine and close SAPO-34 molecular screen membrane on supporter, and each component molar ratio used in Synthesis liquid is P2O5/
Al2O3=0.7~1.0, SiO2/Al2O3=0.3~0.6, DEA/Al2O3=1.5~2.5, H2O/Al2O3=70~150.It is made
Standby obtained SAPO-34 molecular screen membrane is to CO2/CH4Separation has an efficient separating property, but SAPO-34 molecular sieve is prepared into
This height limits it in the industrial applications in UF membrane field.Patent CN 201310516468.1 discloses a kind of macromolecule-
Functional mesoporous SiO 2 hybrid film and preparation method and application, the hybridized film are embedding by polyoxyethylene-polycaprolactam
Section copolymer and functional mesoporous silica composition, preparation process are first by the meso-porous titanium dioxide of polyethyleneimine amino-functionalization
Silicon is added to polyoxyethylene-polycaprolactam block copolymer solution and casting solution is made, and film is then made again；Preparation process letter
Single, the functional mesoporous SiO 2 hybrid film of macromolecule-obtained is used for CO2/CH4Preferable separating property is shown when separation,
CO2Infiltration coefficient reaches 1046barrer, CO2/CH4Separation selectivity is up to 39.5, block copolymer used in the patent and mesoporous oxygen
The equal higher cost of SiClx, is unfavorable for industrialized production.
EMT molecular sieve has three-dimensional twelve-ring pore canal system structure, for other FAU type molecular sieves, EMT points
Sub- sifter device has more flourishing cellular structure and more preferably surface nature, in CO2/CH4There is huge application value in separation.
Molecular screen membrane is also due to its mechanical strength is big, physico-chemical property is stable, high pressure resistant high temperature, regenerating easily, long service life and acidproof
The advantages that alkali corruption is lit up, and attract attention.
So far, few preparations about EMT molecular screen membrane are reported.Chen little Yuan etc., which is reported, utilizes silane coupling agent
Modified FAU/EMT composite membrane has studied the different silane coupler modified influences to the compound film properties of FAU/EMT in document,
And it is applied to CO2/CH4Separate (Xiao yuan chen, Mixed matrix membranes of aminosilanes
grafted FAU/EMT zeolite and cross-linked polyimide for CO2/CH4separation,2012,
53:3269-3280)；As molecular sieve amount 25wt%, when modified with 6FDA-ODA, preparation-obtained FAU/EMT composite membrane CO2/
CH4Separating property is best, but this method needs to operate in anhydrous conditions, and operating process is complicated, is unfavorable for industrialized production.Specially
Sharp 107983176 A of CN discloses a kind of preparation method of EMT molecular screen membrane for the separation of C8 aromatic isomer, which divides
Sub- sieve membrane is to prepare porous hollow fiber ceramic membrane by raw material of aluminium oxide, with polyacrylamide, polyethylene glycol, benzene sulfonamide
The film pretreating agent that hydrochlorate etc. is formed with alkaline silicon source pre-processes ceramic membrane surface, using secondary growth method in ceramic membrane
Surface prepares multilayer EMT molecular sieve, and the EMT molecular screen membrane being prepared has good C8 aromatic isomer separating property, but
The preparation yield rate of film is unable to satisfy requirement in this method.
Nevertheless, EMT molecular screen membrane technology disclosed in above-mentioned patent and document is not used to from CO2/CH4In isolate
CO2To obtain the CH of high-purity4.In addition, the integrality of EMT molecular screen membrane structure is to CO2/CH4Separating effect generate it is huge
Influence.Therefore, synthesize continuous closely knit, thickness uniformly, flawless, pore-size distribution is narrow, bond strength is high and not easily to fall off
For CO2/CH4The EMT molecular sieve ceramic membrane of adsorbing separation is the huge technical problem faced at present, and how to solve EMT points
Combination between sub- sieve membrane and ceramic monolith is its root problem, and the selection of support modification auxiliary agent and its modification mode are weights
Want factor.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of EMT molecular screen membrane and
Preparation method and application, it is modified using cationic polymer surface, binder can be served as on the one hand to improve crystal seed and pottery
Adhesion strength between porcelain supporter, on the other hand can improve the electronegativity on ceramic monolith surface, to improve ceramic monolith table
The dispersing uniformity of face crystal seed.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of EMT molecular screen membrane, using following steps:
Step 1: ceramic supporting body pre-processes: ceramic supporting body being cut, polish, clean, is dried, is subsequently placed in
200~650 DEG C of 0.5~12h of Muffle kiln roasting；After cooling, ceramic supporting body is placed in the solution of cation-containing copolymer
In, and immersion treatment 1min~12h at room temperature~100 DEG C, it takes out the cationic polymer of washing removal excess surface and does
It is dry, obtain pretreated ceramic supporting body；
Step 2: prepared by molecular sieve seed liquid: according to Al2O3:SiO2: template: H2The molar ratio of O is 1:(1~10):
(1~15): the ratio of (100~300) weighs silicon source, silicon source, template, is then completely dissolved in deionized water under stiring
In, obtained sol solutions are finally poured into closed crystallization in ptfe autoclave, it is washed and adjust pH and can be obtained point
Son sieve crystal seed liquid；
Step 3: crystal seed precoating: pretreated ceramic supporting body being immersed in molecular sieve seed liquid, using dipping
The ceramic supporting body surface of czochralski process after the pre-treatment coats molecular sieve seed, obtains being coated with molecular sieve crystalline substance after low temperature drying
The ceramic supporting body of kind；
Step 4: hydrothermal crystallizing: the ceramic supporting body for being coated with molecular sieve seed is placed in Al2O3:Na2O:SiO2: template
Agent: H2O is 1:(0.1~10 in molar ratio): (1~50): (0~1.0): the Zeolite synthesis liquid that (20~400) are mixed to get
In, EMT molecular sieve ceramic membrane is made in crystallization 10~20 days at 100~160 DEG C after drying, calcination activation.
Cationic polymer described in step 1 includes diallyl dimethyl ammoniumchloride, poly- amidine, polyvinylamine, sun from
Sub- polyacrylamide or poly- Hydroxypropyldimonium Chloride, the solution of the cationic polymer are to take water as a solvent to be made into quality
The solution that concentration is 0.5~15%.
As preferred embodiment, cationic polymer uses diallyl dimethyl ammoniumchloride or poly- hydroxypropyl two
One of ammonio methacrylate or combination.
The temperature of immersion treatment described in step 1 is room temperature~60 DEG C, and the time is 1min~2h.
Ceramic supporting body described in step 1 is tubular porous supporter, is single channel or multi-channel structure, material
By one of aluminium oxide, magnesia, zirconium oxide, titanium oxide or silica or it is a variety of form, preferably self-alumina, zirconium oxide or
Titanium oxide.
The average pore size of the ceramic supporting body is 2~5 μm, and porosity is 30%~50%, is single channel or multi-channel
Structure, outer diameter are 12~100mm, and internal diameter is 3~50mm.
Preferably, be single-pass configuration when, outer diameter 12mm, internal diameter 8mm；When for 7 channel design, outer diameter is
30mm, internal diameter 6mm；When for 19 channel design, outer diameter 30mm, internal diameter 4mm；When for 37 channel design, outer diameter is
30mm, internal diameter 3mm.
Ceramic supporting body described in step 1 first carries out rough grinding with the sand paper of 100~600 mesh, then again with 1200~
The sand paper of 2500 mesh carries out smart polishing.
Molecular sieve seed liquid described in step 2 is prepared using following methods: silicon source and template are dissolved under stiring
In deionized water, silicon source is added at 0~80 DEG C, persistently stirs 0.1~10h and obtains sol solutions；It pours into reaction kettle, 90~
120 DEG C of closed crystallization 4h~10 day centrifuge washing 1~6 time, adjust sol solutions pH to 9 with 0.01~1mol/L ammonium hydroxide, are prepared into
To molecular sieve seed liquid.
Molecular sieve seed liquid described in step 2 is the FAU type molecular sieve seed liquid other than EMT, the crystal seed liquid group
Dividing molar ratio is Al2O3:SiO2: template: H2O=1:(2.5~6.0): (3.0~7.0): (100~200).
Source of aluminium includes aluminium hydroxide, hydrated alumina, Aluminum sol, sodium aluminate, aluminum sulfate, aluminium isopropoxide, aluminum phosphate
Or one of bauxite or a variety of mixing,
The silicon source include solid silicone, sodium silicate solid, waterglass, silica solution, tetraethyl orthosilicate, methyl orthosilicate,
One of ethyl orthosilicate, potassium silicate, calcium silicates or white carbon black or a variety of mixing,
The template is tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetraethyl bromination
One of ammonium, 4-propyl bromide, diethylamine, ammonium hydroxide, n-butylamine or pyridine or a variety of mixing.
As preferred embodiment, template uses ammonium hydroxide, tetraethyl ammonium hydroxide or tetrapropyl hydrogen-oxygen
Change one of ammonium or more.
The coating method that step 3 carries out crystal seed coating is vertical Best-Effort request, and dipping time is 1~3 time, is impregnated every time
Time be 0.5~5min；Low temperature drying temperature is room temperature~50 DEG C.
Mole group of Zeolite synthesis liquid described in step 4 becomes Al2O3:Na2O:SiO2: template: H2O=1:(2~
8): (8~30): (0~1.0): (80~200)；The sodium source is sodium oxide molybdena, sodium hydroxide or sodium carbonate, preferably hydroxide
Sodium.
Template described in step 4 is one of 15-crown-5,6 ether of 18- crown-, polyethylene glycol or polyquaternium -6
Or a variety of mixing, for calcination activation controlled at 400~600 DEG C, activation time is 2~8h.
In the EMT molecular sieve ceramic membrane being prepared, molecular sieve thicknesses of layers is 3~4 μm, EMT molecule in molecular sieve layer
The partial size of sieve is 1.5~2 μm, and the average pore size of molecular sieve is 1.8~2.5nm, and specific surface area is 580~640m2/g。
The EMT molecular screen membrane being prepared is in CO2/CH4Application in separation, this kind of molecular screen membrane have higher CO2It inhales
Attached capacity and αCO2/CH4Separation still has higher and more stable decarburization efficiency, lesser mass transfer resistance after absorption-desorption
Power, lower energy consumption and stronger power of regeneration, make it in CO2/CH4Continuous operation can be achieved in adsorbing separation.
The application method of EMT molecular screen membrane are as follows: tubular type EMT molecular sieve ceramic membrane materials are installed in membrane module side by side,
And with epoxy silicone circle seal molecular sieve ceramic membrane both ends, needed before first use to the EMT molecular sieve ceramic membrane after installation into
Row activation；Then, CO is allowed2/CH4Film side of the mixed raw material air-flow through EMT molecular sieve ceramic membrane materials, the infiltration after adsorbing separation
Gas is flowed out from the other side of film, and the higher CH of purity after separation can be obtained4Gas.
The activation and regeneration method of EMT molecular screen membrane are as follows: vacuum available desorption or regeneration gas heating and blowing.
Ceramic supporting body is passed through into cationic polymer surface preparation first in the present invention, then ceramics after modification
Supporting body surface precoating molecular sieve seed is finally placed in closed crystallization in Synthesis liquid, and EMT molecular sieve membrane material can be prepared
Material.EMT molecular screen membrane CO in being applied to natural gas2/CH4When adsorbing separation, has higher CO2Adsorption capacity and
αCO2/CH4Separation.The lesser resistance to mass tranfer of EMT molecular screen membrane, lower energy consumption and stronger power of regeneration, make it in CO2/
CH4Continuous operation can be achieved in adsorbing separation, and it is easily de- to substantially improve ceramic tube surface molecular screen layers in transportational process
The shortcomings that falling.
The present invention combines surface chemical modification with physics coating processes, synthesizes molecular sieve bore diameter narrowly distributing, film layer
Thickness uniformly, flawless and continuity is good and bond strength height, EMT zeolite membrane material not easily to fall off, the EMT molecular screen membrane
Having an excellent mechanical strength, low resistance to mass tranfer while high heat resistance, is also equipped with higher CO2Adsorption capacity and
αCO2/CH4Separation.In addition, the EMT zeolite membrane material is also equipped with lower regeneration temperature, stronger regeneration is reused
Performance.
Compared with prior art, the invention has the characteristics that:
1) compared with existing EMT molecular screen membrane technology of preparing, the present invention use for the first time cationic polymer it is modified with
The method that diauxic growth combines prepares EMT molecular screen membrane.Surface is carried out to ceramic supporting body with cationic polymer to change
Property, not only optimizes the roughness on ceramic supporting body surface, and ceramic supporting body surface after modification form it is abundant
Group significantly improves the hydrophily and electronegativity on ceramic supporting body surface, the load capacity of molecular sieve seed has been effectively ensured；
2) compared with the crystal seed paint-on technique of traditional EMT molecular screen membrane preparation process, the present invention is in ceramic support body surface
The crystal seed of face coating is non-isomorphous molecular sieve seed.
3) compared with existing EMT molecular screen membrane, the EMT molecular screen membrane that the present invention is prepared not only mechanical strength
Height, the binding force between EMT molecular sieve and ceramic supporting body is strong, and the closely knit company of EMT molecular sieve of ceramic supporting body area load
Continuous uniform, thickness reaches 3~4 μm, and average grain diameter is 1.5~2 μm；In addition, flawless in obtained EMT molecular sieve layer, more
Be conducive to CO2/CH4Adsorbing separation；
4) with existing CO2/CH4Isolation technics is compared, and the EMT zeolite membrane material that the present invention is prepared does not only reach
Adsorbing separation requirement, and admission space is small, resistance to mass tranfer is low, consume is small, and regeneration energy consumption when reuse is low, and repetition makes
With high-efficient, in CO2/CH4Continuous operation can be achieved in adsorbing separation.
5) the preparation process simple and stable of EMT zeolite membrane material, early period, device input cost was low, it is easy to accomplish industry
Change.
Detailed description of the invention
Fig. 1 is the SEM figure of EMT molecular sieve powder in the EMT molecular screen membrane being prepared in embodiment 2；
Fig. 2 is BET nitrogen adsorption/desorption of EMT molecular sieve powder in the EMT molecular screen membrane being prepared in embodiment 2
Curve；
Fig. 3 is the SEM figure for the EMT molecular screen membrane being prepared in embodiment 2；
Fig. 4 is that the EMT molecular screen membrane being prepared in embodiment 2 is used for CO2/CH4The breakthrough curve of adsorbing separation.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
A kind of preparation method of EMT molecular screen membrane, using following steps:
Step 1: ceramic supporting body pre-processes: selection tubulose porous supporting body can use single channel or multi-channel knot
Structure is single-pass configuration or multi-channel structure, and the average pore size of the ceramic supporting body of selection is 2~5 μm, porosity is 30%~
50%, material by one of aluminium oxide, magnesia, zirconium oxide, titanium oxide or silica or it is a variety of form, in order to obtain compared with
Good technical effect, material can select aluminium oxide, zirconium oxide or titanium oxide, ceramic supporting body is cut, first with 100~
The sand paper of 600 mesh carries out rough grinding, then carries out smart polishing, cleaning, drying with the sand paper of 1200~2500 mesh again, is subsequently placed in
200~650 DEG C of 0.5~12h of Muffle kiln roasting；After cooling, ceramic supporting body is placed in the solution of cation-containing copolymer
In, it can include diallyl dimethyl ammoniumchloride, poly- amidine in cationic polymer used in this system, polyvinylamine,
Cationic polyacrylamide or poly- Hydroxypropyldimonium Chloride can use polydiene third to obtain preferable technical effect
One of base alkyl dimethyl ammonium chloride or poly- Hydroxypropyldimonium Chloride or combination, take water as a solvent and are made into mass concentration and are
0.5~15% solution, and immersion treatment 1min~12h at room temperature~100 DEG C, can be in order to obtain preferable technical effect
Immersion treatment 1min~2h at room temperature~60 DEG C takes out the cationic polymer of washing removal excess surface and drying, obtains
Pretreated ceramic supporting body
Step 2: prepared by molecular sieve seed liquid: according to Al2O3:SiO2: template: H2The molar ratio of O is 1:(1~10):
(1~15): the ratio of (100~300) weighs silicon source, silicon source, template, or can also be using the FAU type molecule other than EMT
Crystal seed liquid is sieved, this kind of crystal seed liquid component molar ratio is Al2O3:SiO2: template: H2O=1:(2.5~6.0): (3.0~7.0):
(100~200).Silicon source and template are dissolved in deionized water under stiring, silicon source is added at 0~80 DEG C, persistently stirs
It mixes 0.1~10h and obtains sol solutions；It pours into reaction kettle, 90~120 DEG C of closed crystallization 4h~10 day, centrifuge washing 1~6 time, uses
0.01~1mol/L ammonium hydroxide adjusts sol solutions pH to 9, molecular sieve seed liquid is prepared, the silicon source that can be used in this step
Including one of aluminium hydroxide, hydrated alumina, Aluminum sol, sodium aluminate, aluminum sulfate, aluminium isopropoxide, aluminum phosphate or bauxite
Or a variety of mixing, silicon source include solid silicone, sodium silicate solid, waterglass, silica solution, tetraethyl orthosilicate, methyl orthosilicate, just
One of silester, potassium silicate, calcium silicates or white carbon black or a variety of mixing, template are tetramethylammonium hydroxide, tetrem
Base ammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, 4-propyl bromide, diethylamine, ammonium hydroxide, n-butylamine or pyridine
One of or a variety of mixing, can more preferably use ammonium hydroxide, tetraethyl ammonium hydroxide or tetrapropylammonium hydroxide
One of or above be used as template.
Step 3: crystal seed precoating: pretreated ceramic supporting body being immersed in molecular sieve seed liquid, using vertical
The ceramic supporting body surface of Best-Effort request technique after the pre-treatment coats molecular sieve seed, and dipping time is 1~3 time, soaks every time
The time of stain is 0.5~5min, obtains the ceramic supporting body coated with molecular sieve seed after room temperature~50 DEG C are dry；
Step 4: hydrothermal crystallizing: the ceramic supporting body for being coated with molecular sieve seed is placed in Al2O3:Na2O:SiO2: template
Agent: H2O is 1:(0.1~10 in molar ratio): (1~50): (0~1.0): the Zeolite synthesis liquid that (20~400) are mixed to get
In, preferred proportion relation can use 1:(2~8): (8~30): (0~1.0): (80~200), used silicon source,
Silicon source may be the same or different with step 2, and the sodium source used is sodium oxide molybdena, sodium hydroxide or sodium carbonate, and template is
One of 15-crown-5,6 ether of 18- crown-, polyethylene glycol or polyquaternium -6 or a variety of mixing, the crystallization at 100~160 DEG C
10~20 days, EMT molecular sieve ceramic membrane is made afterwards through drying, calcination activation (400~600 DEG C, 2~8h of activation time).
In the EMT molecular sieve ceramic membrane being prepared, molecular sieve thicknesses of layers is 3~4 μm, EMT molecule in molecular sieve layer
The partial size of sieve is 1.5~2 μm, and the average pore size of molecular sieve is 1.8~2.5nm, and specific surface area is 580~640m2/g。
The EMT molecular screen membrane being prepared can be in CO2/CH4Application in separation, this kind of molecular screen membrane have higher
CO2Adsorption capacity and αCO2/CH4Separation still has higher and more stable decarburization efficiency, lesser biography after absorption-desorption
Matter resistance, lower energy consumption and stronger power of regeneration, make it in CO2/CH4Continuous operation can be achieved in adsorbing separation.
The application method of EMT molecular screen membrane are as follows: tubular type EMT molecular sieve ceramic membrane materials are installed in membrane module side by side,
And with epoxy silicone circle seal molecular sieve ceramic membrane both ends, needed before first use to the EMT molecular sieve ceramic membrane after installation into
Row activation；Then, CO is allowed2/CH4Film side of the mixed raw material air-flow through EMT molecular sieve ceramic membrane materials, the infiltration after adsorbing separation
Gas is flowed out from the other side of film, and the higher CH of purity after separation can be obtained4Gas.
The activation and regeneration method of EMT molecular screen membrane are as follows: vacuum available desorption or regeneration gas heating and blowing.
Ceramic supporting body is passed through into cationic polymer surface preparation first in the present invention, then ceramics after modification
Supporting body surface precoating molecular sieve seed is finally placed in closed crystallization in Synthesis liquid, and EMT molecular sieve membrane material can be prepared
Material.EMT molecular screen membrane CO in being applied to natural gas2/CH4When adsorbing separation, has higher CO2Adsorption capacity and
αCO2/CH4Separation.The lesser resistance to mass tranfer of EMT molecular screen membrane, lower energy consumption and stronger power of regeneration, make it in CO2/
CH4Continuous operation can be achieved in adsorbing separation, and it is easily de- to substantially improve ceramic tube surface molecular screen layers in transportational process
The shortcomings that falling.
It is more detailed specific embodiment below.
Embodiment 1:
Ceramic supporting body pretreatment: by average pore size be 2 μm, porosity 30%, outer diameter 12mm, internal diameter are 8mm's
Single channel α-Al2O3Ceramic tube is cut into the short tube of 45mm, is then successively polished smooth with the sand paper of 100 mesh, 1200 mesh,
Deionized water is cleaned by ultrasonic 2h, and dry 3h in 120 DEG C of baking ovens is finally placed in 200 DEG C of Muffle kiln roasting 12h, naturally cools to
Room temperature is spare.
Molecular sieve seed liquid is prepared: by aluminium isopropoxide, silica solution, tetramethylammonium hydroxide, deionized water according to n
(Al2O3):n(SiO2): n (template): n (H2O)=1:2.5:3.5:100 material proportion mixes at room temperature, specific method
Are as follows: first aluminium isopropoxide is dissolved in a part of deionized water, tetramethyl then is added into aluminium isopropoxide solution under stiring
Ammonium hydroxide is denoted as solution A；Silica solution is added in another part deionized water again, stirring 1h makes silica solution be uniformly dispersed,
It is denoted as B solution.B solution is slowly dropped in solution A under room temperature and strong stirring, 0.5h is continuously stirred and sol solutions is made；
Finally sol solutions are transferred in ptfe autoclave, 90 DEG C closed crystallization 10 days, centrifuge washing 1 time, with 0.01mol/L's
Ammonium hydroxide adjusts pH and molecular sieve seed liquid can be obtained for 9.
Crystal seed coating: pretreated α-Al is blocked2O3Ceramic tube both ends, then by α-Al2O3Ceramic tube is dipped vertically into
0.5min is impregnated in above-mentioned molecular sieve seed liquid, finally slowly by α-Al2O3Ceramic tube takes out from crystal seed liquid and does at room temperature
It is dry.
EMT molecular screen membrane preparation: by aluminium isopropoxide, sodium hydroxide, silica solution, 15-crown-5, deionized water according to n
(Al2O3):n(Na2O):n(SiO2): n (template): n (H2O)=1:2.1:10:0.5:100 material proportion mixes at room temperature
Prepare Zeolite synthesis liquid.It is coated with the α-Al of molecular sieve seed2O3Ceramic tube is placed in prepared Zeolite synthesis liquid,
Crystallization 20 days at 100 DEG C, taking out drying and roasting 2h at 400 DEG C can be prepared by EMT molecular screen membrane.
EMT molecular screen membrane is used for CO2/CH4Breakthrough curve (the unstripped gas: CO of adsorbing separation2With CH4Molar ratio be 40:
60, operation pressure 100kPa, total flow 100ml/min) show the CH in 90s4It is adsorbed on EMT molecular screen membrane first
Saturation, and be detected from working off one's feeling vent one's spleen, concentration builds rapidly to peak, quickly increases from the molar fraction 60% in unstripped gas
Be added to 97.5%, and maintain 810s or so.After 845s, CO2Start largely to be detected in working off one's feeling vent one's spleen, until complete after 980s
It penetrates entirely, exports wherein CO2Molar fraction reaches 40%, EMT molecular screen membrane CO absorption2Reach saturation.
Embodiment 2:
Ceramic supporting body pretreatment: by average pore size being 2 μm, porosity 30%, outer diameter 100mm, internal diameter 50mm
Single channel α-Al2O3Ceramic tube is cut into the short tube of 45mm, then successively carries out polishing light with the sand paper of 100 mesh, 1200 mesh
Sliding, deionized water is cleaned by ultrasonic 2h, and dry 3h in 120 DEG C of baking ovens is finally placed in 200 DEG C of Muffle kiln roasting 12h, natural cooling
It is spare to room temperature.α-the Al that will be polished smooth2O3Ceramic tube is placed in the polydiene propyltrimethylammonium chloride that mass concentration is 0.5%
In aqueous ammonium, immersion treatment 1min, takes out α-Al later at room temperature2O3Ceramic tube and the polymer for washing removal excess surface
Cation, last 60 DEG C of drying for standby.
Molecular sieve seed liquid is prepared: by aluminium isopropoxide, silica solution, tetramethylammonium hydroxide, deionized water according to n
(Al2O3):n(SiO2): n (template): n (H2O)=1:2.5:3.5:100 material proportion mixes at room temperature, specific method
Are as follows: first aluminium isopropoxide is dissolved in a part of deionized water, tetramethyl then is added into aluminium isopropoxide solution under stiring
Ammonium hydroxide is denoted as solution A；Silica solution is added in another part deionized water again, stirring 1h makes silica solution be uniformly dispersed,
It is denoted as B solution.B solution is slowly dropped in solution A under room temperature and strong stirring, 0.5h is continuously stirred and sol solutions is made；
Finally sol solutions are transferred in ptfe autoclave, 90 DEG C closed crystallization 10 days, centrifuge washing 1 time, with 0.01mol/L's
Ammonium hydroxide adjusts pH and molecular sieve seed liquid can be obtained for 9.
Crystal seed coating: pretreated α-Al is blocked2O3Ceramic tube both ends, then by α-Al2O3Ceramic tube is dipped vertically into
0.5min is impregnated in above-mentioned molecular sieve seed liquid, finally slowly by α-Al2O3Ceramic tube takes out from crystal seed liquid and does at room temperature
It is dry.
EMT molecular screen membrane preparation: by aluminium isopropoxide, sodium hydroxide, silica solution, 15-crown-5, deionized water according to n
(Al2O3):n(Na2O):n(SiO2): n (template): n (H2O)=1:2.1:10:0.5:100 material proportion mixes at room temperature
Prepare Zeolite synthesis liquid.It is coated with the α-Al of molecular sieve seed2O3Ceramic tube is placed in prepared Zeolite synthesis liquid,
Crystallization 20 days at 100 DEG C, taking out drying and roasting 2h at 400 DEG C can be prepared by EMT molecular screen membrane.It is surveyed later
Examination, SEM and BET nitrogen adsorption/desorption curve test result difference are as shown in Figure 1 and Figure 2.The EMT molecular sieve grain being prepared
Diameter is 1~1.5 μm, specific surface area 599.5m2/g.Kong Rongwei 0.347cm3/g。
Fig. 3 is the SEM figure for the EMT molecular screen membrane being prepared: (a) therein is longitudinal section；It (b) is cross-sectional view；
Fig. 4 is that the EMT molecular screen membrane being prepared is used for CO2/CH4Breakthrough curve (the unstripped gas: CO of adsorbing separation2With CH4Mole
Than being 3 for the preparation-obtained EMT molecular sieve thicknesses of layers of 40:60, operation pressure 100kPa, total flow 100ml/min)
~4 μm, EMT molecular sieve particle size distribution is uniform, and partial size is 1.5~2 μm, and does not observe horizontal and vertical crackle
In the presence of.The separation breakthrough curve of Fig. 4 shows the CH in 95s4The adsorption saturation on EMT molecular screen membrane first, and from working off one's feeling vent one's spleen
It is detected, concentration builds rapidly to peak, is increased rapidly to 98% from the molar fraction in unstripped gas 60%, and maintain
800s or so.After 850s, CO2Start largely to be detected in working off one's feeling vent one's spleen, until complete penetration after 950s, exports wherein CO2It rubs
You reach 40%, EMT molecular screen membrane CO absorption by score2Reach saturation.
Embodiment 3:
Ceramic supporting body pretreatment: by average pore size be 5 μm, porosity 50%, outer diameter 12mm, internal diameter are 8mm's
Single channel α-Al2O3Ceramic tube is cut into the short tube of 45mm, is then successively polished smooth with the sand paper of 600 mesh, 2500 mesh,
Deionized water is cleaned by ultrasonic 4h, and dry 4h in 110 DEG C of baking ovens is finally placed in 650 DEG C of Muffle kiln roasting 1h, naturally cools to room
Warm standby is used.α-the Al that will be polished smooth2O3It is water-soluble that ceramic tube is placed in the polydiene hydroxypropyltrimonium chloride that mass concentration is 15%
In liquid, immersion treatment 5min, takes out α-Al later at room temperature2O3Ceramic tube and the polymer cation for washing removal excess surface,
Last drying for standby at room temperature.
Molecular sieve seed liquid is prepared: by aluminium isopropoxide, silica solution, tetramethylammonium hydroxide, deionized water according to n
(Al2O3):n(SiO2): n (template): n (H2O)=1:5:15:200 material proportion mixing, method particularly includes: first by isopropanol
Aluminium is dissolved in a part of deionized water, and tetramethylammonium hydroxide then is added into aluminium isopropoxide solution under stiring, is denoted as A
Solution；Silica solution is added in another part deionized water again, stirring 1h makes silica solution be uniformly dispersed, and is denoted as B solution.80
DEG C and strong stirring under B solution is slowly dropped in solution A, continuously stir 1h be made sol solutions；Finally sol solutions are transferred to
In ptfe autoclave, 120 DEG C of closed crystallization 4h, centrifuge washing 6 times, adjusting pH with the ammonium hydroxide of 0.01mol/L is 9
Obtain molecular sieve seed liquid.
Crystal seed coating: pretreated α-Al is blocked2O3Ceramic tube both ends, then by α-Al2O3Ceramic tube is dipped vertically into
5min is impregnated in above-mentioned molecular sieve seed liquid, finally slowly by α-Al2O3Ceramic tube takes out from crystal seed liquid and dries at room temperature.
EMT molecular screen membrane preparation: by aluminium isopropoxide, sodium hydroxide, silica solution, 15-crown-5, deionized water according to n
(Al2O3):n(Na2O):n(SiO2): n (template): n (H2O)=1:2.1:10:0.8:120 material proportion mixes at room temperature
Prepare Zeolite synthesis liquid.It is coated with the α-Al of molecular sieve seed2O3Ceramic tube is placed in prepared Zeolite synthesis liquid,
Crystallization 10 days at 160 DEG C, taking out drying and roasting 4h at 400 DEG C can be prepared by EMT molecular screen membrane.
EMT molecular screen membrane is used for CO2/CH4Breakthrough curve (the unstripped gas: CO of adsorbing separation2With CH4Molar ratio be 30:
70, operation pressure 100kPa, total flow 100ml/min) show the CH in 80s4It is adsorbed on EMT molecular screen membrane first
Saturation, and be detected from working off one's feeling vent one's spleen, concentration builds rapidly to peak, quickly increases from the molar fraction 70% in unstripped gas
Be added to 98.1%, and maintain 790s or so.After 820s, CO2Start largely to be detected in working off one's feeling vent one's spleen, until complete after 860s
It penetrates entirely, exports wherein CO2Molar fraction reaches 30%, EMT molecular screen membrane CO absorption2Reach saturation.
Embodiment 4:
Ceramic supporting body pretreatment: by average pore size being 5 μm, porosity 40%, outer diameter 30mm, 7 that internal diameter is 6mm
Channel α-Al2O3Ceramic tube is cut into the short tube of 45mm, is then successively polished smooth, is gone with the sand paper of 600 mesh, 2500 mesh
Ionized water is cleaned by ultrasonic 4h, and dry 4h in 110 DEG C of baking ovens is finally placed in 500 DEG C of Muffle kiln roasting 4h, naturally cools to room temperature
It is spare.α-the Al that will be polished smooth2O3Ceramic tube is placed in the polydiene hydroxypropyltrimonium chloride aqueous solution that mass concentration is 10%
In, immersion treatment 3min, takes out α-Al later at room temperature2O3Ceramic tube and the polymer cation for washing removal excess surface, most
Drying for standby at room temperature afterwards.
Molecular sieve seed liquid is prepared: by aluminium isopropoxide, silica solution, tetramethylammonium hydroxide, deionized water according to n
(Al2O3):n(SiO2): n (template): n (H2O)=1:2.5:7.0:200 material proportion mixing, method particularly includes: it first will be different
Aluminium propoxide is dissolved in a part of deionized water, and tetramethylammonium hydroxide then is added into aluminium isopropoxide solution under stiring,
It is denoted as solution A；Silica solution is added in another part deionized water again, stirring 1h makes silica solution be uniformly dispersed, and it is molten to be denoted as B
Liquid.B solution is slowly dropped in solution A under 60 DEG C and strong stirring, 1h is continuously stirred and sol solutions is made；Finally by colloidal sol
Liquid is transferred in ptfe autoclave, 120 DEG C closed crystallization 5 days, centrifuge washing 3 times, adjusting pH with the ammonium hydroxide of 1mol/L is 9
Molecular sieve seed liquid can be obtained.
Crystal seed coating: pretreated α-Al is blocked2O3Ceramic tube both ends, then by α-Al2O3Ceramic tube is dipped vertically into
5min is impregnated in above-mentioned molecular sieve seed liquid, finally slowly by α-Al2O3Ceramic tube takes out from crystal seed liquid and dries at room temperature.
EMT molecular screen membrane preparation: by aluminium isopropoxide, sodium hydroxide, silica solution, 15-crown-5, deionized water according to n
(Al2O3):n(Na2O):n(SiO2): n (template): n (H2O)=1:2.1:10:0.5:120 material proportion mixes at room temperature
Prepare Zeolite synthesis liquid.It is coated with the α-Al of molecular sieve seed2O3Ceramic tube is placed in prepared Zeolite synthesis liquid,
Crystallization 8 days at 140 DEG C, taking out drying and roasting 4h at 400 DEG C can be prepared by EMT molecular screen membrane.
EMT molecular screen membrane is used for CO2/CH4Breakthrough curve (the unstripped gas: CO of adsorbing separation2With CH4Molar ratio be 40:
60, operation pressure 100kPa, total flow 100ml/min) show the CH in 96s4It is adsorbed on EMT molecular screen membrane first
Saturation, and be detected from working off one's feeling vent one's spleen, concentration builds rapidly to peak, quickly increases from the molar fraction 60% in unstripped gas
Be added to 98.5%, and maintain 815s or so.After 855s, CO2Start largely to be detected in working off one's feeling vent one's spleen, until complete after 970s
It penetrates entirely, exports wherein CO2Molar fraction reaches 40%, EMT molecular screen membrane CO absorption2Reach saturation.
Embodiment 5:
Ceramic supporting body pretreatment: by average pore size being 3 μm, porosity 30%, outer diameter 30mm, 7 that internal diameter is 3mm
Channel α-ZrO2Ceramic tube is cut into the short tube of 45mm, is then successively polished smooth, is gone with the sand paper of 400 mesh, 2000 mesh
Ionized water is cleaned by ultrasonic 4h, and dry 4h in 110 DEG C of baking ovens is finally placed in 550 DEG C of Muffle kiln roasting 4h, naturally cools to room temperature
It is spare.α-the ZrO that will be polished smooth2Ceramic tube is placed in the poly- Hydroxypropyldimonium Chloride aqueous solution that mass concentration is 10%
In, immersion treatment 3min, takes out α-ZrO later at room temperature2Ceramic tube and the polymer cation for washing removal excess surface, most
Drying for standby at room temperature afterwards.
Molecular sieve seed liquid is prepared: by aluminium isopropoxide, tetraethyl orthosilicate, tetramethylammonium hydroxide, deionized water according to n
(Al2O3):n(SiO2): n (template): n (H2O)=1:2.5:7.0:200 material proportion mixing, method particularly includes: it first will be different
Aluminium propoxide is dissolved in a part of deionized water, and tetramethylammonium hydroxide then is added into aluminium isopropoxide solution under stiring,
It is denoted as solution A；Tetraethyl orthosilicate is added in another part deionized water again, stirring 1h makes silica solution be uniformly dispersed, and is denoted as B
Solution.B solution is slowly dropped in solution A under 60 DEG C and strong stirring, 1h is continuously stirred and sol solutions is made；It finally will be molten
Glue is transferred in ptfe autoclave, 120 DEG C closed crystallization 5 days, centrifuge washing 5 times, adjusted with the ammonium hydroxide of 0.5mol/L
Molecular sieve seed liquid can be obtained for 9 in pH.
Crystal seed coating: pretreated α-ZrO is blocked2Ceramic tube both ends, then by α-ZrO2Ceramic tube is dipped vertically into
It states and impregnates 2min in molecular sieve seed liquid, finally slowly by α-ZrO2Ceramic tube takes out from crystal seed liquid and dries at room temperature.
EMT molecular screen membrane preparation: by aluminium isopropoxide, sodium hydroxide, silica solution, 6 ether of 18- crown-, deionized water according to n
(Al2O3):n(Na2O):n(SiO2): n (template): n (H2O)=1:2.1:10:0.5:150 material proportion mixes at room temperature
Prepare Zeolite synthesis liquid.It is coated with the α-Al of molecular sieve seed2O3Ceramic tube is placed in prepared Zeolite synthesis liquid,
Crystallization 15 days at 110 DEG C, taking out drying and roasting 5h at 550 DEG C can be prepared by EMT molecular screen membrane.
EMT molecular screen membrane is used for CO2/CH4Breakthrough curve (the unstripped gas: CO of adsorbing separation2With CH4Molar ratio be 40:
60, operation pressure 100kPa, total flow 100ml/min) show the CH in 90s4It is adsorbed on EMT molecular screen membrane first
Saturation, and be detected from working off one's feeling vent one's spleen, concentration builds rapidly to peak, quickly increases from the molar fraction 60% in unstripped gas
Be added to 98.0%, and maintain 810s or so.After 840s, CO2Start largely to be detected in working off one's feeling vent one's spleen, until complete after 950s
It penetrates entirely, exports wherein CO2Molar fraction reaches 40%, EMT molecular screen membrane CO absorption2Reach saturation.
Embodiment 6:
Ceramic supporting body pretreatment: by average pore size be 3 μm, porosity 30%, outer diameter 50mm, internal diameter are 20mm's
7 channel α-TiO2Ceramic tube is cut into the short tube of 45mm, is then successively polished smooth, is gone with the sand paper of 400 mesh, 2000 mesh
Ionized water is cleaned by ultrasonic 4h, and dry 4h in 110 DEG C of baking ovens is finally placed in 550 DEG C of Muffle kiln roasting 4h, naturally cools to room temperature
It is spare.α-the TiO that will be polished smooth2Ceramic tube is placed in the poly- Hydroxypropyldimonium Chloride aqueous solution that mass concentration is 10%
In, immersion treatment 3min, takes out α-TiO later at room temperature2Ceramic tube and the polymer cation for washing removal excess surface, most
Drying for standby at room temperature afterwards.
Molecular sieve seed liquid is prepared: by aluminium isopropoxide, tetraethyl orthosilicate, tetraethyl ammonium hydroxide, deionized water according to n
(Al2O3):n(SiO2): n (template): n (H2O)=1:2.5:7.0:200 material proportion mixing, method particularly includes: it first will be different
Aluminium propoxide is dissolved in a part of deionized water, and tetramethylammonium hydroxide then is added into aluminium isopropoxide solution under stiring,
It is denoted as solution A；Tetraethyl orthosilicate is added in another part deionized water again, stirring 1h makes silica solution be uniformly dispersed, and is denoted as B
Solution.B solution is slowly dropped in solution A under 60 DEG C and strong stirring, 1h is continuously stirred and sol solutions is made；It finally will be molten
Glue is transferred in ptfe autoclave, 100 DEG C closed crystallization 5 days, centrifuge washing 5 times, adjusted with the ammonium hydroxide of 0.5mol/L
Molecular sieve seed liquid can be obtained for 9 in pH.
Crystal seed coating: pretreated α-TiO is blocked2Ceramic tube both ends, then by α-TiO2Ceramic tube is dipped vertically into
It states and impregnates 2min in molecular sieve seed liquid, finally slowly by α-TiO2Ceramic tube takes out from crystal seed liquid and dries at room temperature.
EMT molecular screen membrane preparation: by aluminium hydroxide, sodium hydroxide, tetraethyl orthosilicate, 6 ether of 18- crown-, deionized water according to
n(Al2O3):n(Na2O):n(SiO2): n (template): n (H2O)=1:2.1:10:1.0:150 material proportion mixes at room temperature
Prepare Zeolite synthesis liquid.It is coated with the α-Al of molecular sieve seed2O3Ceramic tube is placed in prepared Zeolite synthesis liquid,
Crystallization 20 days at 110 DEG C, taking out drying and roasting 5h at 550 DEG C can be prepared by EMT molecular screen membrane.
EMT molecular screen membrane is used for CO2/CH4Breakthrough curve (the unstripped gas: CO of adsorbing separation2With CH4Molar ratio be 40:
60, operation pressure 100kPa, total flow 100ml/min) show the CH in 90s4It is adsorbed on EMT molecular screen membrane first
Saturation, and be detected from working off one's feeling vent one's spleen, concentration builds rapidly to peak, quickly increases from the molar fraction 60% in unstripped gas
Be added to 97.0%, and maintain 800s or so.After 830s, CO2Start largely to be detected in working off one's feeling vent one's spleen, until complete after 920s
It penetrates entirely, exports wherein CO2Molar fraction reaches 39.5%, EMT molecular screen membrane CO absorption2Reach saturation.
Embodiment 7:
Ceramic supporting body pretreatment: by average pore size be 2 μm, porosity 30%, outer diameter 30mm, internal diameter are 3mm's
37 channel α-Al2O3Ceramic tube is cut into the short tube of 45mm, is then successively polished smooth with the sand paper of 300 mesh, 1800 mesh,
Deionized water is cleaned by ultrasonic 4h, and dry 4h in 110 DEG C of baking ovens is finally placed in 550 DEG C of Muffle kiln roasting 4h, naturally cools to room
Warm standby is used.α-the Al that will be polished smooth2O3Ceramic tube is placed in the poly- Hydroxypropyldimonium Chloride aqueous solution that mass concentration is 15%
In, immersion treatment 3min, takes out α-Al later at room temperature2O3Ceramic tube and the polymer cation for washing removal excess surface, most
Drying for standby at room temperature afterwards.
Molecular sieve seed liquid is prepared: by aluminium isopropoxide, waterglass, tetrapropylammonium hydroxide, deionized water according to n
(Al2O3):n(SiO2): n (template): n (H2O)=1:2.5:7.0:200 material proportion mixing, method particularly includes: it first will be different
Aluminium propoxide is dissolved in a part of deionized water, and tetramethylammonium hydroxide then is added into aluminium isopropoxide solution under stiring,
It is denoted as solution A；Waterglass is added in another part deionized water again, stirring 1h makes silica solution be uniformly dispersed, and it is molten to be denoted as B
Liquid.B solution is slowly dropped in solution A under 50 DEG C and strong stirring, 1h is continuously stirred and sol solutions is made；Finally by colloidal sol
Liquid is transferred in ptfe autoclave, 110 DEG C closed crystallization 20 days, centrifuge washing 2 times, adjust pH with the ammonium hydroxide of 0.1mol/L
Molecular sieve seed liquid can be obtained for 9.
Crystal seed coating: pretreated α-TiO is blocked2Ceramic tube both ends, then by α-Al2O3Ceramics are dipped vertically into
It states and impregnates 5min in molecular sieve seed liquid, finally slowly by α-Al2O3Ceramics take out from crystal seed liquid and dry at room temperature.
EMT molecular screen membrane preparation: by aluminium hydroxide, sodium hydroxide, tetraethyl orthosilicate, 6 ether of 18- crown-, deionized water according to
n(Al2O3):n(Na2O):n(SiO2): n (template): n (H2O)=1:2.1:10:1.0:150 material proportion mixes at room temperature
Prepare Zeolite synthesis liquid.It is coated with the α-Al of molecular sieve seed2O3Ceramic tube is placed in prepared Zeolite synthesis liquid,
Crystallization 20 days at 110 DEG C, taking out drying and roasting 5h at 550 DEG C can be prepared by EMT molecular screen membrane.
EMT molecular screen membrane is used for CO2/CH4Breakthrough curve (the unstripped gas: CO of adsorbing separation2With CH4Molar ratio be 40:
60, operation pressure 100kPa, total flow 100ml/min) show the CH in 90s4It is adsorbed on EMT molecular screen membrane first
Saturation, and be detected from working off one's feeling vent one's spleen, concentration builds rapidly to peak, quickly increases from the molar fraction 60% in unstripped gas
Be added to 97.6%, and maintain 790s or so.After 820s, CO2Start largely to be detected in working off one's feeling vent one's spleen, until complete after 950s
It penetrates entirely, exports wherein CO2Molar fraction reaches 40%, EMT molecular screen membrane CO absorption2Reach saturation.
Embodiment 8:
In the present embodiment, template is changed to 6 ether of 18- crown- and polyethylene glycol in Synthesis liquid, and mass ratio 1:1, remaining is the same as real
Apply example 7.
The EMT molecular screen membrane is used for CO2/CH4Breakthrough curve (the unstripped gas: CO of adsorbing separation2With CH4Molar ratio be
40:60, operation pressure 100kPa, total flow 100ml/min) show the CH in 90s4It is inhaled on EMT molecular screen membrane first
Attached saturation, and be detected from working off one's feeling vent one's spleen, concentration builds rapidly to peak, quick from the molar fraction 60% in unstripped gas
Increase to 99.0%, and maintain 840s or so.After 860s, CO2Start largely to be detected in working off one's feeling vent one's spleen, until 1000s
Complete penetration afterwards exports wherein CO2Molar fraction reaches 40%, EMT molecular screen membrane CO absorption2Reach saturation.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (16)
1. a kind of preparation method of EMT molecular screen membrane, which is characterized in that this method uses following steps:
Step 1: ceramic supporting body pre-processes: ceramic supporting body is cut, polished, cleaned, is dried, it is subsequently placed in 200~
650 DEG C of 0.5~12h of Muffle kiln roasting；After cooling, ceramic supporting body is placed in the solution of cation-containing copolymer, and
Immersion treatment 1min~12h at room temperature~100 DEG C takes out the cationic polymer of washing removal excess surface and drying, obtains
To pretreated ceramic supporting body；
Step 2: prepared by molecular sieve seed liquid: according to Al2O3:SiO2: template: H2The molar ratio of O is 1:(1~10): (1~
15): the ratio of (100~300) weighs silicon source, silicon source, template, is then completely dissolved in deionized water under stiring, most
Obtained sol solutions are poured into closed crystallization in reaction kettle afterwards, it is washed and adjust pH molecular sieve seed liquid can be obtained；
Step 3: crystal seed precoating: pretreated ceramic supporting body being immersed in molecular sieve seed liquid, using Best-Effort request
The ceramic supporting body surface of technique after the pre-treatment coats molecular sieve seed, is obtained after low temperature drying coated with molecular sieve seed
Ceramic supporting body；
Step 4: hydrothermal crystallizing: the ceramic supporting body for being coated with molecular sieve seed is placed in Al2O3:Na2O:SiO2: template:
H2O is 1:(0.1~10 in molar ratio): (1~50): (0~1.0): in the Zeolite synthesis liquid that (20~400) are mixed to get,
EMT molecular sieve ceramic membrane is made in crystallization 10~20 days at 100~160 DEG C after drying, calcination activation.
2. a kind of preparation method of EMT molecular screen membrane according to claim 1, which is characterized in that sun described in step 1
Ionomer includes diallyl dimethyl ammoniumchloride, poly- amidine, polyvinylamine, cationic polyacrylamide or poly- hydroxypropyl
Alkyl dimethyl ammonium chloride, the solution of the cationic polymer are to take water as a solvent to be made into the solution that mass concentration is 0.5~15%.
3. a kind of preparation method of EMT molecular screen membrane according to claim 1 or 2, which is characterized in that the cation
One of the preferred diallyl dimethyl ammoniumchloride of polymer or poly- Hydroxypropyldimonium Chloride or combination.
4. a kind of preparation method of EMT molecular screen membrane according to claim 1, which is characterized in that soaked described in step 1
The temperature of bubble processing is room temperature~60 DEG C, and the time is 1min~2h.
5. a kind of preparation method of EMT molecular screen membrane according to claim 1, which is characterized in that described in step 1
Ceramic supporting body be tubular porous supporter, be single channel or multi-channel structure, material by aluminium oxide, magnesia, zirconium oxide,
One of titanium oxide or silica or a variety of compositions, preferably self-alumina, zirconium oxide or titanium oxide.
6. a kind of preparation method of EMT molecular screen membrane according to claim 5, which is characterized in that the ceramic supporting body
Average pore size be 2~5 μm, porosity be 30%~50%, be single channel or multi-channel structure, outer diameter be 12~100mm,
Internal diameter is 3~50mm.
7. a kind of preparation method of EMT molecular screen membrane according to claim 1, which is characterized in that make pottery described in step 1
Porcelain supporter first carries out rough grinding with the sand paper of 100~600 mesh, then carries out smart polishing with the sand paper of 1200~2500 mesh again.
8. a kind of preparation method of EMT molecular screen membrane according to claim 1, which is characterized in that divide described in step 2
Son sieve crystal seed liquid is prepared using following methods: silicon source and template being dissolved in deionized water under stiring, at 0~80 DEG C
Silicon source is added, persistently stirs 0.1~10h and obtains sol solutions；It pours into reaction kettle, 90~120 DEG C of closed crystallization 4h~10 day, from
The heart washs 1~6 time, adjusts sol solutions pH to 9 with 0.01~1mol/L ammonium hydroxide, molecular sieve seed liquid is prepared.
9. according to claim 1 with a kind of preparation method of EMT molecular screen membrane described in 8, which is characterized in that described in step 2
Molecular sieve seed liquid be EMT other than FAU type molecular sieve seed liquid, the crystal seed liquid component molar ratio be Al2O3:SiO2:
Template: H2O=1:(2.5~6.0): (3.0~7.0): (100~200).
10. a kind of preparation method of EMT molecular screen membrane described according to claim 1 or 8 or 9, which is characterized in that
Source of aluminium includes aluminium hydroxide, hydrated alumina, Aluminum sol, sodium aluminate, aluminum sulfate, aluminium isopropoxide, aluminum phosphate or aluminium
One of alumina or a variety of mixing,
The silicon source includes solid silicone, sodium silicate solid, waterglass, silica solution, tetraethyl orthosilicate, methyl orthosilicate, positive silicon
One of acetoacetic ester, potassium silicate, calcium silicates or white carbon black or a variety of mixing,
The template is tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, four
One of propyl ammonium bromide, diethylamine, ammonium hydroxide, n-butylamine or pyridine or a variety of mixing.
11. a kind of preparation method of EMT molecular screen membrane described according to claim 1 or 8 or 9, which is characterized in that the template
One of the preferred ammonium hydroxide of agent, tetraethyl ammonium hydroxide or tetrapropylammonium hydroxide or more.
12. a kind of preparation method of EMT molecular screen membrane according to claim 1, which is characterized in that step 3 carries out crystal seed
The coating method of coating is vertical Best-Effort request, and dipping time is 1~3 time, and the time impregnated every time is 0.5~5min；Low temperature
Drying temperature is room temperature~50 DEG C.
13. a kind of preparation method of EMT molecular screen membrane according to claim 1, which is characterized in that divide described in step 4
Mole group of son sieve Synthesis liquid becomes Al2O3:Na2O:SiO2: template: H2O=1:(2~8): (8~30): (0~1.0): (80
~200)；The sodium source is sodium oxide molybdena, sodium hydroxide or sodium carbonate, preferably sodium hydroxide.
14. a kind of preparation method of EMT molecular screen membrane according to claim 1, which is characterized in that mould described in step 4
Plate agent is one of 15-crown-5,6 ether of 18- crown-, polyethylene glycol or polyquaternium -6 or a variety of mixing, calcination activation control
Temperature is 400~600 DEG C, and activation time is 2~8h.
15. the EMT molecular screen membrane that method as described in claim 1 is prepared, which is characterized in that the EMT molecule being prepared
It sieves in ceramic membrane, molecular sieve thicknesses of layers is 3~4 μm, and the partial size of EMT molecular sieve is 1.5~2 μm in molecular sieve layer, molecular sieve
Average pore size be 1.8~2.5nm, specific surface area be 580~640m2/g。
16. a kind of EMT molecular screen membrane being prepared such as claim 1 is in CO2/CH4Application in separation.
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