CN107335342B - A kind of synthesizer and synthetic method of doughnut type T molecular sieve film - Google Patents
A kind of synthesizer and synthetic method of doughnut type T molecular sieve film Download PDFInfo
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- CN107335342B CN107335342B CN201710796493.8A CN201710796493A CN107335342B CN 107335342 B CN107335342 B CN 107335342B CN 201710796493 A CN201710796493 A CN 201710796493A CN 107335342 B CN107335342 B CN 107335342B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
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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
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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
- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
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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
- 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
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Abstract
The invention discloses a kind of preparation facilities and method of doughnut type T molecular sieve film, 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
Technical field
This application involves a kind of film synthesizer and methods, and in particular to a kind of synthesis of hollow fiber molecular sieve.
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 type T molecular sieve film is most often
One of molecular screen membrane type of infiltration evaporation dehydration of organic solvent seen, the common method of synthesis type T molecular sieve film have conjunction in situ
Cheng Fa, secondary growth method, sol-gal process, plug-hole method and microwave process for synthesizing etc. are a variety of, but most common method surely belongs to original position
Synthetic method and secondary growth method.Above two method is compared, and it is excellent that secondary growth method has that crystallization rate is fast, crystallization rate is controllable etc.
Point, is more advantageous to industrialized production.And the common carrier of type T molecular sieve film is prepared as chip, tubular type and hollow fiber form, still
Only tubular type industrialized at present, wherein chip is only applicable to laboratory research since membrane area is smaller, and doughnut carrier
There is higher specific surface area relative to tubular media, theoretically with better application potential.
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 and synthesis technology of novel doughnut type T molecular sieve film.
Invention content
To solve the above problems, the present invention provides a kind of preparation facilities and method of doughnut type T molecular sieve film.
Wherein, the preparation facilities of doughnut type T molecular sieve film provided by the invention is as follows：
A kind of synthesizer of the T-shaped film of doughnut, it is characterised in that it includes reaction kettle, crystal seed liquid storage tank, air and adds
Thermal, casting solution surge tank, the wherein upper and lower ends of reaction kettle connect one end of feeding line and the pipeline that discharges, charging respectively
The other end of pipeline is gone out by four-way connection A connection crystal seed liquid feeding line, casting solution feeding line and hot-air feed line line
The other end of expects pipe line is discharged pipeline and hot-air vent line by discharge pipeline, casting solution of four-way connection B connection crystal seeds liquid,
Crystal seed liquid feeding line and crystal seed liquid discharging pipeline are connected to the both ends of crystal seed liquid storage tank, and hot-air feed line line is heated with air
Device connection, casting solution feeding line and casting solution discharging pipeline are connected to the both ends of casting solution surge tank；The reaction kettle
It is cylinder, there is feed liquid dispersion area, feed liquid contact zone and feed liquid set area successively from top to bottom, wherein feed liquid contact zone is divided
If spacing body is separated into dry contact channel, single contact channel forms a film for single doughnut carrier crystallization, wherein contacting channel
Internal diameter for 15-20mm, the synthesizer for the doughnut carrier of 1.2-1.8mm outer diameters 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 type T molecular sieve film：
A kind of method for synthesizing T-shaped hollow-fibre membrane, it is characterised in that this method includes crystal seed coating, carrier drying, load
Body crystallization process；Wherein,
The crystal seed coating step is：T-shaped crystal seed liquid is delivered in crystal seed liquid storage tank, doughnut carrier is fixed
In in contact channel, valve V71, V72 are opened, makes that crystal seed liquid passes sequentially through crystal seed liquid feeding line, feeding line enters reaction
In kettle, and through discharging pipeline and crystal seed liquid discharging pipeline is back to crystal seed liquid storage tank, after specified coating time to be achieved, close
Valve V71, and close valve V72 after crystal seed liquid completely returns to crystal seed liquid storage tank and complete a crystal seed coating procedure；
The carrier drying process is：Valve V73, V74 are opened, the hot-air generated in air heating apparatus leads to successively
Overfire air feeding line and feeding line enter the doughnut carrier after reaction kettle coats crystal seed and are dried, and dry
Hot-air afterwards after specified drying time to be achieved, is closed by pipeline and the hot-air vent line progress emptying process of discharging
Valve closing door V73, V74；
The carrier crystallization process is：In fresh casting film liquid storage tank prepare containing silicon source, silicon source, Na2O, K2O and
The casting solution of water is inputted by valve V79 in casting solution surge tank, and opening valve V75, valve V76, valve V78 makes casting solution lead to successively
It crosses casting solution feeding line and feeding line enters in reaction kettle, and enter through discharging pipeline and discarded casting solution discharging pipeline and give up
It abandons in casting film liquid storage tank, after specified washing time to be achieved, closes valve V78, open valve V77 so that casting film by crystallization
Liquid recycles, and after one section of specified crystallization time to be achieved, is again switched off valve V77, opens valve V78 so that casting solution entrance is useless
It abandons in casting film liquid storage tank.It is to be appreciated that it is because crystal seed liquid can remain in pipe to a certain extent why to set cleaning step
On line, 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
The pollution of film liquid, therefore the part casting solution is not recycled in casting solution surge tank as possible.It certainly, can be in the casting solution of pollution
When meeting crystallization needs, the cleaning step can not need to, so as to directly carry out crystallization so that production cost is minimum.
Preferably, the type T molecular sieve grain diameter for preparing crystal seed liquid is 0.7-1.5 μm, and a crystal seed coating time is 5-
30s, crystal seed coating step repeat 0-3 times, drying time 6-24h.
Preferably, washing time 5-100s, casting solution temperature are 60~120 DEG C；One crystallization time for 0.5~
4 h；Carrier crystallization steps repeat 0~3 time.
Doughnut type T molecular sieve film prepared in accordance with the present invention, can be used for dehydration of organic solvent, and described is organic
The one kind of solvent in alcohol, ketone, aldehyde, ester, furans, pyridine.
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 hollow by the present invention
Fiber carrier crystallization film forming contact channel, pass through control contact channel internal diameter and feed liquid flow velocity so that casting solution with
The mode of similar cross-flow filtration is along doughnut carrier flow, so that molecular screen membrane particle in casting solution and miscellaneous
Matter is difficult to adhering to carrier surface so as to utmostly ensure that crystallization degree.
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 type T molecular sieve film of technical solution of the present invention synthesis, characterize and tie by Pervaporation Technology
Fruit shows that in operation temperature be 70 DEG C, when feed liquid is the ethanol/water solution system that water content is 5wt.%, the separation of the film because
Sub- ＞ 4000, flux ＞ 1.5kgh-1m-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 type T molecular sieve film 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 illustrate the essential structure of the present invention in a schematic way, therefore it only shows composition related to the present invention.
Fig. 1 be the T-shaped film of doughnut synthesizer, including reaction kettle 1, crystal seed liquid storage tank 2, air heating apparatus 3,
Casting solution surge tank 4, the wherein upper and lower ends of reaction kettle 1 connect one end of feeding line and the pipeline that discharges, feeding line respectively
The other end by four-way connection A10-1 connection crystal seed liquid feeding line, casting solution feeding line and hot-air feed line line, go out
The other end of expects pipe line is emptied by four-way connection B10-2 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 2, 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 4；Reaction kettle
1 is cylinder, has feed liquid dispersion area 1-1, feed liquid contact zone 1-2 and feed liquid set area 1-3, feed liquid contact successively from top to bottom
If area 1-2 is separated into dry contact channel 1-6, single contact channel 1-6 for single 11 crystalline substance of doughnut carrier by separator 1-5
Film is melted into, there is fixing piece 1-4 doughnut carrier is fixed in feed liquid contact zone for feed liquid contact zone 1-2 both sides, contact
The internal diameter of channel 1-6 is 18mm, and synthesizer forms a film for the crystallization of the doughnut carrier of 1.5mm outer diameters.
There is valve V71 7-1, pump P8-1 8-1 and flowmeter F9-1 9-1, hot-air feed line on crystal seed liquid feeding line
On line there is valve V73 7-3, wind turbine 8-2 and flowmeter F92 9-2, there is valve V75 7- successively on casting solution feeding line
5th, P8-3 8-3 and flowmeter F9-3 9-3 are pumped, crystal seed liquid discharging pipeline, hot-air vent line and casting solution discharge on pipeline
There is valve V72 7-2, V74 7-4, V76 7-6 successively.Casting solution surge tank 4 by fresh casting solution feed pipe with it is fresh
Casting film liquid storage tank 5 connects, and has valve V79 7-9 on fresh casting solution feed pipe.Have three to connect on casting solution discharging pipeline
Head 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 giving up
The connection of casting solution pipeline is abandoned, wherein being provided with valve V77 7-7, valve V78 7- on cycle casting solution pipeline and discarded casting solution pipeline
8 .Reaction kettle outer wall has insulating layer 1-7, and separator 1-5 is by stainless steel integrated molding.
The method that doughnut type T molecular sieve film is prepared using above-mentioned steps is as follows：
1. crystal seed liquid is prepared
By homemade type T molecular sieve particle（Average grain diameter 0.8um）It is a concentration of that crystal seed liquid is mixed with water（2 wt.%）
Crystal seed liquid, and through ultrasound, be input in crystal seed liquid storage tank after stir process 10min.
2. crystal seed coats
By doughnut carrier（Aoxidize aluminium material, outer diameter 1.5mm）The fixation of reaction kettle is fixed on after impregnating, drying
On part.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 passes through
Discharging pipeline 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 to crystal seed liquid storage tank and completes a crystal seed coating procedure.
3. carrier drying
Open valve V73, V74, the hot-air generated in air heating apparatus pass sequentially through hot-air feed line line and into
Expects pipe line enters the doughnut carrier after reaction kettle coats crystal seed and is dried, and dried hot-air passes through discharge nozzle
Line and hot-air vent line carry out emptying process, after 12h, close valve V73, V74.
Repetitive coatings step and carrier drying step 1 time.
4. casting solution is prepared
After NaOH and KOH are dissolved completely in deionized water, NaAlO2 is added in, is slowly added dropwise after solution clarification into silicon
Colloidal sol is aged 12h at room temperature, the component molar of casting solution than SiO2: Al2O3: Na2O: K2O: H2O 24: 1: 8: 2: 600,
And it is 100 DEG C to set heating temperature.It is inputted in casting solution surge tank 4 by valve V79 7-9.
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 20s
Afterwards, valve V78 7-8 are closed, open valve V77 7-7 so that the casting solution by crystallization recycles, after 4h to be achieved, again
It closes valve V77 7-7, open 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
Type T molecular sieve film after crystallization from reaction kettle is taken out, is rinsed repeatedly with deionized water, and impregnate 6h in water
After be put into baking oven and 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 water content is 5wt.%
During alcohol/water solution system, the separation factor 5000 of the film, flux 1.6kgh-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 synthesizer of doughnut type T molecular sieve film, it is characterised in that it includes reaction kettle（1）, crystal seed liquid storage tank
（2）, air heating apparatus（3）, casting solution surge tank（4）, wherein reaction kettle（1）Upper and lower ends connect respectively feeding line and
One end of discharging pipeline, the other end of feeding line pass through four-way connection A（10-1）Connect crystal seed liquid feeding line, casting solution into
Expects pipe line and hot-air feed line line, the other end for the pipeline that discharges pass through four-way connection B（10-2）Connection 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 connect with air heating apparatus, and casting solution feeding line is connected with casting solution discharging pipeline
In casting solution surge tank（4）Both ends；The reaction kettle（1）It is cylinder, there is feed liquid dispersion area successively from top to bottom（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 forms a film, wherein contact is logical
Road（1-6）Internal diameter for 15-20mm, the synthesizer for the doughnut carrier of 1.2-1.8mm outer diameters crystallization film forming.
2. the apparatus according to claim 1, wherein crystal seed liquid feeding line, hot-air feed line line and casting solution feed pipe
There is valve V71 successively on line（7-1）、V73（7-3）、V75（7-5）, crystal seed liquid discharging pipeline, hot-air vent line and casting film
There is valve V72 successively on liquid discharging pipeline（7-2）、V74（7-4）、V76（7-6）.
3. the apparatus of claim 2, it is characterised 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）.
4. device according to claim 3, it is characterised 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）.
5. the apparatus according to claim 1, it is characterised in that reaction kettle outer wall has insulating layer（1-7）, separator（1-5）
By stainless steel integrated molding.
6. the apparatus according to claim 1, it is characterised 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.
7. a kind of method that device according to claim 4 synthesizes T-shaped hollow-fibre membrane, it is characterised in that this method includes
Crystal seed coating, carrier drying, carrier crystallization process；Wherein, the crystal seed coating step is：T-shaped crystal seed liquid is delivered to crystalline substance
Kind liquid storage tank（2）In, doughnut carrier is fixed on contact channel（1-6）It is interior, open valve V71, V72, make crystal seed liquid according to
It is secondary that reaction kettle is entered by crystal seed liquid feeding line, feeding line（1）In, and through pipeline and the discharging pipeline return of crystal seed liquid of discharging
To crystal seed liquid storage tank（2）, after specified coating time to be achieved, valve V71 is closed, and treat that crystal seed liquid completely returns to crystal seed liquid
Storage tank（2）Valve V72 is closed afterwards completes a crystal seed coating procedure；The carrier drying process is：Opening valve V73,
V74, air heating apparatus（3）The hot-air of middle generation passes sequentially through hot-air feed line line and feeding line enters reaction kettle
（1）Doughnut carrier after being coated to crystal seed is dried, and dried hot-air passes through pipeline and the hot-air row of discharging
Blank pipe line carries out emptying process, after specified drying time to be achieved, closes valve V73, V74；The carrier crystallization process
For：In fresh casting film liquid storage tank（5）It is middle to prepare containing silicon source, silicon source, Na2O、K2The casting solution of O and water pass through valve V79（7-
9）Input casting solution surge tank（4）In, open valve V75（7-5）, valve V76（7-6）, valve V78（7-8）Pass sequentially through casting solution
Casting solution feeding line and feeding line enter reaction kettle（1）In, and through pipeline and the discharging pipeline entrance of discarded casting solution of discharging
Discarded casting film liquid storage tank（6）In, after specified washing time to be achieved, close valve V78（7-8）, open valve V77 (7-7) with
Make to recycle by the casting solution of crystallization, after one section of specified crystallization time to be achieved, be 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.
8. according to the method described in claim 7, it is characterized in that the type T molecular sieve grain diameter for preparing crystal seed liquid is 0.7-
1.5 μm, a crystal seed coating time is 5-30s, and crystal seed coating step repeats 0-3 times, drying time 6-24h.
9. according to the method described in claim 7, it is characterized in that washing time is 5-100s, casting solution temperature is 60~120
℃；One crystallization time is 0.5~4 h；Carrier crystallization steps repeat 0~3 time.
10. application of the hollow fiber molecular sieve prepared according to the method for claim 8 in terms of dehydration of organic solvent,
The one kind of the organic solvent in alcohol, ketone, aldehyde, ester, furans, pyridine.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810542811.2A CN108465384A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer of doughnut type T molecular sieve film |
| CN201710796493.8A CN107335342B (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut type T molecular sieve film |
| CN201810541220.3A CN108786480B (en) | 2017-09-06 | 2017-09-06 | Synthesizer of molecular sieve membrane for pharmaceutical chemical industry |
| CN201810542824.XA CN108786481A (en) | 2017-09-06 | 2017-09-06 | The synthesizer of doughnut type T molecular sieve film |
| CN201810541231.1A CN108816060A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer of medication chemistry molecular screen membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710796493.8A CN107335342B (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut type T molecular sieve film |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810541220.3A Division CN108786480B (en) | 2017-09-06 | 2017-09-06 | Synthesizer of molecular sieve membrane for pharmaceutical chemical industry |
| CN201810541231.1A Division CN108816060A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer of medication chemistry molecular screen membrane |
| CN201810542811.2A Division CN108465384A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer of doughnut type T molecular sieve film |
| CN201810542824.XA Division CN108786481A (en) | 2017-09-06 | 2017-09-06 | The synthesizer of doughnut type T molecular sieve film |
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| Publication Number | Publication Date |
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| CN107335342A CN107335342A (en) | 2017-11-10 |
| CN107335342B true CN107335342B (en) | 2018-06-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810541231.1A Withdrawn CN108816060A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer of medication chemistry molecular screen membrane |
| CN201810541220.3A Active CN108786480B (en) | 2017-09-06 | 2017-09-06 | Synthesizer of molecular sieve membrane for pharmaceutical chemical industry |
| CN201710796493.8A Active CN107335342B (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut type T molecular sieve film |
| CN201810542811.2A Withdrawn CN108465384A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer of doughnut type T molecular sieve film |
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| CN108031299B (en) * | 2018-01-27 | 2019-12-17 | 浙江汇甬新材料有限公司 | synthesizer of economic nature molecular sieve membrane |
| CN111054222B (en) * | 2019-11-29 | 2021-11-19 | 宁波大学 | Successive transfer synthesis method of molecular sieve membrane |
| CN113457471B (en) * | 2021-08-05 | 2024-01-26 | 安徽工程大学 | Molecular sieve membrane and preparation method and application thereof |
| CN115057452A (en) * | 2022-07-10 | 2022-09-16 | 苏州科技大学 | Method for rapidly preparing molecular sieve and molecular sieve membrane by using 'clean' crystal seeds |
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| CN102166480A (en) * | 2011-03-01 | 2011-08-31 | 南京九思高科技有限公司 | An apparatus and a method for synthesizing molecular sieve membranes |
| CN102527258A (en) * | 2012-01-19 | 2012-07-04 | 大连理工大学 | Preparation method for T-type zeolite molecular sieve membrane |
| CN105056769A (en) * | 2015-07-21 | 2015-11-18 | 江苏九天高科技股份有限公司 | Method and device for preparation of NaA zeolite membrane |
| CN106139914A (en) * | 2016-08-25 | 2016-11-23 | 江苏九天高科技股份有限公司 | The preparation method of a kind of molecular screen membrane and device |
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| US6287432B1 (en) * | 1987-03-13 | 2001-09-11 | The Standard Oil Company | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions |
| US6180168B1 (en) * | 1999-02-01 | 2001-01-30 | Air Products And Chemicals, Inc. | Process for the manufacture of a membrane device with internal sweep |
| JP2004076087A (en) * | 2002-08-15 | 2004-03-11 | Univ Waseda | Manufacturing method and manufacturing apparatus for silicon oxide-based ceramic film by vapor phase synthesis method |
| JP2009066462A (en) * | 2005-12-28 | 2009-04-02 | Asahi Kasei Chemicals Corp | Method for preparing composite membrane |
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| CN102166480A (en) * | 2011-03-01 | 2011-08-31 | 南京九思高科技有限公司 | An apparatus and a method for synthesizing molecular sieve membranes |
| CN102527258A (en) * | 2012-01-19 | 2012-07-04 | 大连理工大学 | Preparation method for T-type zeolite molecular sieve membrane |
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| CN108816060A (en) | 2018-11-16 |
| CN108786480B (en) | 2021-06-15 |
| CN108786481A (en) | 2018-11-13 |
| CN107335342A (en) | 2017-11-10 |
| CN108465384A (en) | 2018-08-31 |
| CN108786480A (en) | 2018-11-13 |
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