CN108176244A - A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes - Google Patents

A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes Download PDF

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CN108176244A
CN108176244A CN201810075546.1A CN201810075546A CN108176244A CN 108176244 A CN108176244 A CN 108176244A CN 201810075546 A CN201810075546 A CN 201810075546A CN 108176244 A CN108176244 A CN 108176244A
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crystal seed
casting solution
valve
pipeline
casting
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李晨舒
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    • 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
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0076—Pretreatment of inorganic membrane material prior to membrane formation, e.g. coating of metal powder
    • 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
    • B01D67/0039—Inorganic membrane manufacture
    • 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
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • 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
    • B01D69/08—Hollow fibre membranes
    • 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

Abstract

The invention discloses a kind of preparation facilities and method of 1 molecular screen membranes of doughnut Silicalite, it is by traditional reaction kettle by channels separated into several contact channels for single doughnut carrier crystallization, and the internal diameter for contacting channel is optimized in a manner of casting solution to be made to pass through similar cross-flow filtration by doughnut carrier according to multiple parameters such as casting film fluid viscosities, avoiding sieve particle in casting solution influences the crystallization of carrier, and pass through rational technological design and can carry out crystal seed coating successively in a kettle, carrier drying and crystallization steps, avoid phenomenon of rupture of the doughnut carrier in moving process.

Description

A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes
Technical field
This application involves a kind of film synthesizer and methods, and in particular to a kind of doughnut silicalite-1 molecular sieves The synthesis of film.
Background technology
In field of medicine and chemical technology, the organic solvent of anhydrous grade is essential, therefore will be a small amount of in organic solvent or micro- The water separation of amount is one of most common in pharmaceutical field and most important unit process so as to obtain anhydrous grade organic solvent. The infiltration evaporation membrane technology that recent decades grow up institute during a small amount of or minor amount of water in Separation of Organic by it Intrinsic low energy consumption does not introduce the advantages such as third component, blowdown be few, has obtained the generally approval of people.Infiltration evaporation membrane technology Be one kind using component vapor partial pressure difference in organic solvent as motive force, it is different from diffusion rate by dissolving of each component in film Property come realize mixture separation process.
And in numerous infiltration evaporation membrane materials, the one kind of molecular screen membrane as ceramic membrane, because of the crystal structure of its stabilization There is splendid competitiveness with the pore diameter range infiltration evaporation dehydration of organic solvent aspect of synthesis.And Silicalite-1 molecular sieves Film is one of molecular screen membrane type of most common infiltration evaporation dehydration of organic solvent, is taken off different from common NaA molecular sieve membrane The performance of water, Silicalite-1 are accomplished that dealcoholysis during alcohol-water separation.It is normal to synthesize Silicalite-1 molecular screen membranes The method seen has that in-situ synthesis, secondary growth method, sol-gal process, plug-hole method and microwave process for synthesizing etc. are a variety of, but most often Method surely belongs to in-situ synthesis and secondary growth method.Above two method is compared, secondary growth method have crystallization rate it is fast, The advantages that crystallization rate is controllable is more advantageous to industrialized production.And it prepares the common carrier of Silicalite-1 molecular screen membranes and is Chip, tubular type and hollow fiber form, but industrialized at present only tubular type, wherein chip are only applicable to since membrane area is smaller Laboratory research, and doughnut carrier has higher specific surface area relative to tubular media, theoretically has and preferably should Use potentiality.
The doughnut carrier for being used to prepare hollow fiber molecular sieve is small for the outer diameter of ceramic material, easily fractures, but It is that existing hollow fiber molecular sieve preparation process need to undergo multiple steps such as crystal seed coating, drying, crystallization, and each step There is respective process unit, therefore the doughnut carrier/migration of film geographically inevitably causes to fracture to reduce Qualification rate.
In addition, existing molecular screen membrane crystallizing kettle is often the enlarged version of laboratory room small-sized reaction kettle, then increase wherein Add a stirring, but find in use the complexity of its crystallization process to be far longer than used in laboratory operation it is small Type reaction kettle, wherein, the crystallization molecular screen membrane in large-size reactor, easily fabricated in situ sieve particle in the solution, and be somebody's turn to do Sieve particle easily adheres to carrier surface so as to influence the crystallization process of carrier surface due to the eddy current effect that stirring generates.
It would therefore be highly desirable to need a kind of synthesizer of novel doughnut Silicalite-1 molecular screen membranes and synthesis work Skill.
Invention content
To solve the above problems, the present invention provides a kind of preparation facilities of doughnut Silicalite-1 molecular screen membranes And method.
Wherein, the preparation facilities of doughnut Silicalite-1 molecular screen membranes provided by the invention is as follows：
A kind of synthesizer of doughnut Silicalite-1 films, it is characterised in that it includes reaction kettle, crystal seed liquid storage tank, sky Gas heating unit, casting solution surge tank, the wherein upper and lower ends of reaction kettle connect one end of feeding line and the pipeline that discharges respectively, The other end of feeding line passes through four-way connection A connection crystal seed liquid feeding line, casting solution feeding line and hot-air feed line Line, the other end for the pipeline that discharges are emptied by four-way connection B connection crystal seeds liquid discharging pipeline, casting solution discharging pipeline and hot-air Pipeline, crystal seed liquid feeding line and crystal seed liquid discharging pipeline are connected to the both ends of crystal seed liquid storage tank, hot-air feed line line and sky The connection of gas heating unit, casting solution feeding line and casting solution discharging pipeline are connected to the both ends of casting solution surge tank；Described Reaction kettle is cylinder, has feed liquid dispersion area, feed liquid contact zone and feed liquid set area successively from top to bottom, and wherein feed liquid contacts If area is by channels separated into dry contact channel, single contact channel forms a film for single doughnut carrier crystallization, and contact is logical Road inner wall has hydrophobic coating.The internal diameter of wherein contact channel is 30-50mm, and the synthesizer is used for 1.2-1.8mm outer diameters Doughnut carrier crystallization film forming.
It should be noted that present invention is generally directed to the doughnut carrier of 1.2-1.8mm outer diameters, and the load of various outer diameter Body needs to configure the contact channel of different inner diameters, but is not that simple carrier outer diameter is smaller, and contact channel internal diameter is with regard to smaller Relationship.But according to numerous known parameters such as carrier outer diameter, casting film fluid viscosity to contact channel casting film liquid hydrodynamics into Row is investigated, and adjusts to maximize the quality for ensureing film to carry out the parameters such as internal diameter, casting film flow quantity cooperation.Casting solution is flowing through During doughnut carrier surface, since rational internal diameter designs so that be adhered to the sieve particle or impurity of seed layer/film layer The casting solution flowed subsequently through washes away, but the crystal seed coated in crystal seed coating procedure is due to passing through drying steps and carrier Binding force more by force without being washed.
In addition, the inner wall of contact channel is preferably provided hydrophobic coating so that the inner wall after crystal seed coating step is as possible Crystal seed is not remained, remaining crystal seed will necessarily be grown with carrier, reduce crystal effect.The hydrophobic coating can be with selected as Polyurethane, epoxy resin, silicones, acrylic resin, alkyd resin etc..
Preferably, on crystal seed liquid feeding line, hot-air feed line line and casting solution feeding line successively have valve V71, V73, V75, crystal seed liquid discharging pipeline, hot-air vent line and casting solution discharging pipeline on successively have valve V72, V74, V76.
Preferably, casting solution surge tank is connect by fresh casting solution feed pipe with fresh casting film liquid storage tank, fresh casting film There is valve V79 on liquid feed pipe.Preferably, in fresh casting film liquid storage tank have agitating device, including motor, agitating shaft and Blade.And when autoclave body is larger, it may be considered that multiple agitating devices are set, Vltrasonic device can also be set to coordinate agitating device So that each interface of casting solution keeps homogeneity.And for the heating of casting solution, it can select to set in fresh casting film liquid storage tank Electric heater unit is put, chuck can also be set on the outer wall, it is carried out by media such as silicone oil to be heated to suitable temperature.For Ensure that crystallization temperature meets needs, buffering liquid storage tank can equally set electrical heating or chuck heating unit, and itself and reaction kettle Between pipeline should shorten as possible to avoid heat detract.
Preferably, there is three-way connection on casting solution discharging pipeline, the both ends of outlet respectively with casting solution surge tank, useless It abandons casting film liquid storage tank and is connected by recycling casting solution pipeline with discarded casting solution pipeline, wherein cycle casting solution pipeline and discarded casting Valve V77, valve V78 are provided on film liquid pipeline.
Preferably, reaction kettle outer wall has insulating layer, and separator is by stainless steel integrated molding.Insulating layer is set Purpose is to ensure crystallization temperature, likewise, it can set additional heating unit to ensure crystallization temperature, certainly, reaction kettle Inside has temperature measuring equipment.
Preferably, there is fixing piece doughnut carrier is fixed in feed liquid contact zone for feed liquid contact zone both sides.
It is specific as follows the present invention also provides a kind of preparation method of doughnut Silicalite-1 molecular screen membranes：
A kind of method for synthesizing Silicalite-1 hollow-fibre membranes, it is characterised in that this method includes crystal seed coating, carrier is done Dry, carrier crystallization process；Wherein,
The crystal seed coating step is：Silicalite-1 crystal seed liquid is delivered in crystal seed liquid storage tank, doughnut is carried Body be fixed on contact channel in, open valve V71, V72, make crystal seed liquid pass sequentially through crystal seed liquid feeding line, feeding line into Enter in reaction kettle, and crystal seed liquid storage tank, specified coating time to be achieved are back to through discharging pipeline and crystal seed liquid discharging pipeline Afterwards, valve V71 is closed, and closes valve V72 after crystal seed liquid completely returns to crystal seed liquid storage tank and completes a crystal seed coating Process；
The carrier drying process is：Valve V73, V74 are opened, the hot-air generated in air heating apparatus passes sequentially through heat Air feed pipeline and feeding line enter the doughnut carrier after reaction kettle coats crystal seed and are dried, and dried Hot-air after specified drying time to be achieved, closes valve by pipeline and the hot-air vent line progress emptying process of discharging Door V73, V74；
The carrier crystallization process is：It is prepared in fresh casting film liquid storage tank and contains silicon source, tetrapropylammonium hydroxide and water Casting solution is inputted by valve V79 in casting solution surge tank, and opening valve V75, valve V76, valve V78 makes casting solution pass sequentially through casting Film liquid feeding line and feeding line enter in reaction kettle, and enter discarded casting through discharging pipeline and discarded casting solution discharging pipeline In film liquid storage tank, after specified washing time to be achieved, valve V78 is closed, opens valve V77 so that the casting solution by crystallization follows Ring utilizes, and after one section of specified crystallization time to be achieved, is again switched off valve V77, opens valve V78 so that casting solution enters discarded casting In film liquid storage tank.It is to be appreciated why setting cleaning step can be remained on pipeline to a certain extent because of crystal seed liquid, The influence of residual crystal seed liquid can be reduced by the flushing of casting solution, crystal seed liquid, which is brought into casting solution, causes casting solution Pollution, therefore the part casting solution is not recycled in casting solution surge tank as possible.Certainly, crystalline substance can be met in the casting solution of pollution When change needs, the cleaning step can not need to, so as to directly carry out crystallization so that production cost is minimum.
Preferably, the Silicalite-1 sieve particles grain size for preparing crystal seed liquid is 1.0-1.5 μm, a crystal seed coating Time is 10-30s, and crystal seed coating step repeats 0-3 times, drying time 6-24h.
Preferably, washing time 10-100s, casting solution temperature are 160~200 DEG C；One crystallization time is 0.5 ~4 h；Carrier crystallization steps repeat 0~3 time.
The present invention compares compared with the prior art, has the following advantages：
1. relative to traditional molecular screen membrane reaction kettle, molecular screen membrane is divided into several respectively for single doughnut by the present invention The contact channel of carrier crystallization film forming contacts the internal diameter of channel and the flow velocity of feed liquid by control so that casting solution is with similar The mode of cross-flow filtration is along doughnut carrier flow, so that the molecular screen membrane particle and impurity in casting solution are difficult Utmostly ensure that crystallization degree adhering to carrier surface.
2. it needs to complete crystal seed coating, dry, crystallization in different devices relative to existing hollow fiber molecular sieve Above three step in same device is completed by rational processing arrangement, avoids physical location by process, the present invention Movement lead to the fracture of doughnut carrier, further through suitable container is set to coordinate, ensure that the purity level of casting solution.
3. using the doughnut Silicalite-1 molecular screen membranes of technical solution of the present invention synthesis, by infiltration evaporation Characterized by techniques the result shows that, operation temperature be 70 DEG C, when feed liquid is the ethanol/water solution system that ethanol content is 5wt.%, should The separation factor ＞ 100 of film, flux ＞ 1kgh-1·m-2, with high selectivity and permeation flux.
Description of the drawings
The present invention is further described in conjunction with the accompanying drawings and embodiments：
Fig. 1 is the preparation facilities of the doughnut Silicalite-1 molecular screen membranes of the present invention.
Fig. 2 is the section plan view of the contact channel of reaction kettle shown in FIG. 1.
In figure, 1：Reaction kettle；1-1：Feed liquid dispersion area；1-2：Feed liquid contact zone：1-3：Feed liquid set area；1-4：It is fixed Part；1-5：Cut piece；1-6：Contact channel；1-7：Insulating layer；2：Crystal seed liquid storage tank；3：Air heating apparatus；4：Casting solution delays Rush tank；5：Fresh casting film liquid storage tank；6：Discarded casting film liquid storage tank；7-1：Valve V71；7-2：Valve V72;7-3：Valve V73；7-4：Valve V74；7-5：Valve V75；7-6：Valve V76；7-7：Valve V77；7-8：Valve V78；7-9：Valve V79；8-1：Pump P81；8-2：Wind turbine；8-3： Pump P83；9-1：Flowmeter F91；9-2：Flowmeter F92；9-3：Flowmeter F93；10-1：Four-way connection A；10-2：Four-way connection B；10-3：Three-way connection.
Specific embodiment
The invention will be further described in the following with reference to the drawings and specific embodiments：
It is further details of explanation to the present invention presently in connection with drawings and examples.The attached drawing is simplified schematic diagram, only with Illustration illustrates the essential structure of the present invention, therefore it only shows composition related to the present invention.
Fig. 1 is the synthesizer of doughnut Silicalite-1 films, including reaction kettle 1, crystal seed liquid storage tank 2, air Heating unit 3, casting solution surge tank 4, the wherein upper and lower ends of reaction kettle 1 connect the one of feeding line and discharging pipeline respectively End, the other end of feeding line pass through four-way connection A10-1 connection crystal seed liquid feeding line, casting solution feeding line and hot-air Feeding line, the other end of the pipeline that discharges by four-way connection B10-2 connection crystal seeds liquid discharge pipeline, casting solution discharge pipeline and Hot-air vent line, crystal seed liquid feeding line and crystal seed liquid discharging pipeline are connected to the both ends of crystal seed liquid storage tank 2, hot-air into Expects pipe line is connect with air heating apparatus, and casting solution feeding line and casting solution discharging pipeline are connected to casting solution surge tank 4 Both ends；Reaction kettle 1 is cylinder, has feed liquid dispersion area 1-1, feed liquid contact zone 1-2 and feed liquid set area successively from top to bottom 1-3, if feed liquid contact zone 1-2 is separated into dry contact channel 1-6 by separator 1-5, single contact channel 1-6 is for single hollow 11 crystallization of fiber carrier forms a film, and contact channel 1-6 inner walls have hydrophobic coating, and feed liquid contact zone 1-2 both sides have fixing piece 1-4 Doughnut carrier is fixed in feed liquid contact zone, the internal diameter of contact channel 1-6 is 45mm, and synthesizer is used for 1.8mm The crystallization film forming of the doughnut carrier of outer diameter.
There is valve V71 7-1, pump P81 8-1 and flowmeter F91 9-1, hot-air feed line line on crystal seed liquid feeding line It is upper that there is valve V73 7-3, wind turbine 8-2 and flowmeter F92 9-2, have successively on casting solution feeding line valve V75 7-5, Pump P83 8-3 and flowmeter F93 9-3, crystal seed liquid discharging pipeline, hot-air vent line and casting solution discharging pipeline on according to It is secondary that there is valve V72 7-2, V74 7-4, V76 7-6.Casting solution surge tank 4 passes through fresh casting solution feed pipe and fresh casting Film liquid storage tank 5 connects, and has valve V79 7-9 on fresh casting solution feed pipe.There is three-way connection on casting solution discharging pipeline 10-3, the both ends of outlet are respectively with casting solution surge tank 4, discarded casting film liquid storage tank 6 by recycling casting solution pipeline and discarding Casting solution pipeline connects, wherein being provided with valve V77 7-7, valve V78 7-8 on cycle casting solution pipeline and discarded casting solution pipeline .Reaction kettle outer wall has insulating layer 1-7, and separator 1-5 is by stainless steel integrated molding.
The method that doughnut SILICALITE molecular screen membranes are prepared using above-mentioned steps is as follows：
1. crystal seed liquid is prepared
By homemade Silicalite-1 sieve particles（Average grain diameter 1um）It is a concentration of that crystal seed liquid is mixed with water（2 wt.%）Crystal seed liquid, and add the hydroxypropyl cellulose of 0.5wt% as binding agent, and defeated after ultrasound, stir process 10min Enter into crystal seed liquid storage tank.
2. crystal seed coats
By doughnut carrier（Aoxidize aluminium material, outer diameter 1.8mm）The fixing piece of reaction kettle is fixed on after impregnating, drying On.Valve V71, V72 are opened, makes that crystal seed liquid passes sequentially through crystal seed liquid feeding line, feeding line enters in reaction kettle, and through going out Expects pipe line and crystal seed liquid discharging pipeline are back to crystal seed liquid storage tank, after 30s, close valve V71, and treat that crystal seed liquid completely returns to Valve V72 is closed after crystal seed liquid storage tank and completes a crystal seed coating procedure.
3 carrier dryings
Valve V73, V74 are opened, the hot-air generated in air heating apparatus passes sequentially through hot-air feed line line and feed pipe Line enter reaction kettle to crystal seed coat after doughnut carrier be dried, and dried hot-air by discharge pipeline and Hot-air vent line carries out emptying process, after 12h, closes valve V73, V74.
Repetitive coatings step and carrier drying step 1 time.
4. casting solution is prepared
Using Ludox as silicon source, tetrapropylammonium hydroxide is template, and SiO2: TPAOH: H2O=1 is configured to deionized water: The casting solution of 0.17: 120 (molar ratio) at room temperature after aging, is inputted by valve V79 7-9 in casting solution surge tank 4.
5. carrier crystallization
Opening valve V75 7-5, valve V76 7-6, valve V78 7-8 makes casting solution pass sequentially through casting solution feeding line and charging Pipeline enters in reaction kettle 1, and enters in discarded casting film liquid storage tank 6 through discharging pipeline and discarded casting solution discharging pipeline, treats After 20s, valve V78 7-8 are closed, open valve V77 7-7 so that the casting solution by crystallization recycles, after 4h to be achieved, It is again switched off valve V77 7-7, opens valve V78 7-8 so that casting solution enters in discarded casting film liquid storage tank 6.
Repeat carrier drying and carrier crystallization steps 1 time.
6. post processing
Silicalite-1 molecular screen membranes after crystallization from reaction kettle are taken out, are rinsed repeatedly, and in water with deionized water Baking oven is put into after immersion 6h to be dried for standby.
7. performance characterization
Show that in operation temperature be 70 DEG C by Pervaporation Technology characterization result, feed liquid is the second that ethanol content is 5wt.% During alcohol/water solution system, the separation factor 110 of the film, flux 1.2kgh-1·m-2。
The foregoing is merely highly preferred embodiment of the present invention, are not intended to restrict the invention.It is all the present invention principle and Any modification, equivalent substitution, improvement and etc. done within spirit, should be included within the scope of the present invention.

Claims (10)

  1. A kind of 1. method for synthesizing Silicalite-1 hollow-fibre membranes, it is characterised in that this method includes crystal seed coating, carrier Dry, carrier crystallization process；The synthesizer that wherein this method uses includes reaction kettle（1）, crystal seed liquid storage tank（2）, air adds Thermal（3）, casting solution surge tank（4）, wherein reaction kettle（1）Upper and lower ends respectively connect feeding line and the pipeline that discharges One end, the other end of feeding line pass through four-way connection A（10-1）Connect crystal seed liquid feeding line, casting solution feeding line and heat Air feed pipeline, the other end for the pipeline that discharges pass through four-way connection B（10-2）Connect crystal seed liquid discharging pipeline, casting solution discharging Pipeline and hot-air vent line, crystal seed liquid feeding line and crystal seed liquid discharging pipeline are connected to crystal seed liquid storage tank（2）Both ends, Hot-air feed line line is connect with air heating apparatus, and casting solution feeding line and casting solution discharging pipeline are connected to casting solution and delay Rush tank（4）Both ends.
  2. 2. the according to the method described in claim 1, reaction kettle described in its feature（1）It is cylinder, have successively from top to bottom Feed liquid dispersion area（1-1）, feed liquid contact zone（1-2）With feed liquid set area（1-3）, wherein feed liquid contact zone（1-2）By separator （1-5）If it is separated into dry contact channel（1-6）, single contact channel（1-6）For single doughnut carrier（11）Crystallization into Film contacts channel（1-6）Inner wall has hydrophobic coating；Wherein contact channel（1-6）Internal diameter for 30-50mm, the synthesis dress Put the crystallization film forming of the doughnut carrier for 1.2-1.8mm outer diameters.
  3. 3. according to the method described in claim 1, it is characterized in that wherein crystal seed liquid feeding line, hot-air feed line line and casting There is valve V71 successively on film liquid feeding line（7-1）、V73（7-3）、V75（7-5）, crystal seed liquid discharging pipeline, hot-air emptying There is valve V72 successively on pipeline and casting solution discharging pipeline（7-2）、V74（7-4）、V76（7-6）.
  4. 4. according to the method described in claim 2, it is characterized in that casting solution surge tank（4）By fresh casting solution feed pipe with Fresh casting film liquid storage tank（5）It connects, there is valve V79 on fresh casting solution feed pipe（7-9）.
  5. 5. according to the method described in claim 2, it is characterized in that there is three-way connection on casting solution discharging pipeline（10-3）, The both ends of outlet respectively with casting solution surge tank（4）, discarded casting film liquid storage tank（6）By recycling casting solution pipeline and discarded casting film Liquid pipe line connects, wherein being provided with valve V77 on cycle casting solution pipeline and discarded casting solution pipeline（7-7）, valve V78（7-8）.
  6. 6. according to the method described in claim 2, it is characterized in that reaction kettle outer wall has insulating layer（1-7）, separator（1-5） By stainless steel integrated molding.
  7. 7. according to the method described in claim 2, it is characterized in that feed liquid contact zone（1-2）Both sides have fixing piece（1-4）With Doughnut carrier is fixed in feed liquid contact zone.
  8. 8. according to the method described in claim 1, it is characterized in that the crystal seed coating step is：By Silicalite-1 crystalline substances Kind liquid is delivered to crystal seed liquid storage tank（2）In, doughnut carrier is fixed on contact channel（1-6）It is interior, opening valve V71, V72, makes that crystal seed liquid passes sequentially through crystal seed liquid feeding line, feeding line enters in reaction kettle, and through pipeline and the crystal seed liquid of discharging Discharging pipeline is back to crystal seed liquid storage tank, after specified coating time to be achieved, closes valve V71, and treat that crystal seed liquid returns completely Closing valve V72 completes a crystal seed coating procedure after being back to crystal seed liquid storage tank；The carrier drying process is：Open valve Door V73, V74, the hot-air generated in air heating apparatus passes sequentially through hot-air feed line line and feeding line enters reaction Doughnut carrier after kettle coats crystal seed is dried, and dried hot-air passes through pipeline and the hot-air emptying of discharging Pipeline carries out emptying process, after specified drying time to be achieved, closes valve V73, V74；The carrier crystallization process is： In fresh casting film liquid storage tank（5）Middle casting solution of the preparation containing silicon source, template and water, passes through valve V79（7-9）Input casting film Liquid surge tank（4）In, open valve V75（7-5）, valve V76（7-6）, valve V78（7-8）Casting solution is made to pass sequentially through casting solution charging Pipeline and feeding line enter in reaction kettle, and enter discarded casting film liquid storage tank through discharging pipeline and discarded casting solution discharging pipeline （6）In, after specified washing time to be achieved, close valve V78（7-8）, valve V77 (7-7) is opened so that casting by crystallization Film liquid recycles, and after one section of specified crystallization time to be achieved, is again switched off valve V77（7-7）, open valve V78（7-8）So that Casting solution enters discarded casting film liquid storage tank（6）In.
  9. 9. according to the method described in claim 7, it is characterized in that prepare the Silicalite-1 sieve particle grains of crystal seed liquid Diameter is 0.5-2 μm, and a crystal seed coating time is 10-30s, and crystal seed coating step repeats 0-3 times, drying time 6-24h.
  10. 10. according to the method described in claim 1, it is characterized in that washing time is 20-100s, casting solution temperature for 160~ 200℃；One crystallization time is 0.5~4 h；Carrier crystallization steps repeat 0~3 time.
CN201810075546.1A 2017-09-06 2017-09-06 A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes Withdrawn CN108176244A (en)

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Application publication date: 20180619