CN107362695B - A kind of synthesizer and synthetic method of the molecular screen membranes of doughnut Silicalite 1 - Google Patents
A kind of synthesizer and synthetic method of the molecular screen membranes of doughnut Silicalite 1 Download PDFInfo
- Publication number
- CN107362695B CN107362695B CN201710797610.2A CN201710797610A CN107362695B CN 107362695 B CN107362695 B CN 107362695B CN 201710797610 A CN201710797610 A CN 201710797610A CN 107362695 B CN107362695 B CN 107362695B
- Authority
- CN
- China
- Prior art keywords
- crystal seed
- casting solution
- valve
- line
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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 the molecular screen membranes of doughnut Silicalite 1, it is by traditional reactor by channels separated into some contact passages for single doughnut carrier crystallization, and the internal diameter for contacting passage is optimized according to multiple parameters such as casting film fluid viscosities and passes through doughnut carrier in a manner of making casting solution by similar cross-flow filtration, avoid sieve particle in casting solution influences on the crystallization of carrier, and crystal seed coating can be carried out successively by rational technological design in a kettle, carrier drying and crystallization steps, avoid phenomenon of rupture of the doughnut carrier in moving process.
Description
Technical field
The application is related to a kind of film synthesizer and method, 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 level is essential, therefore will be a small amount of in organic solvent or micro-
The water separation of amount, it is one of most common in pharmaceutical field and most important unit process so as to obtain anhydrous level 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, the advantages such as third component, blowdown be few are not introduced, 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 its stable crystal structure
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 normal
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, it is more beneficial for industrialized production.And prepare the conventional carrier of Silicalite-1 molecular screen membranes and be
Chip, tubular type and hollow fiber form, but industrialized at present only tubular type, wherein chip are only applicable to because membrane area is smaller
Laboratory research, and doughnut carrier has higher specific surface area relative to tubular media, has preferably should in theory
Use potentiality.
It is small for the external diameter of ceramic material for preparing the doughnut carrier of hollow fiber molecular sieve, easily fracture, but
It is that existing hollow fiber molecular sieve preparation technology 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 causes to fracture so as to reduce unavoidably
Qualification rate.
In addition, existing molecular screen membrane crystallizing kettle is often the enlarged version of laboratory room small-sized reactor, 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 reactor, 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 eddy current effect caused by stirring.
It would therefore be highly desirable to need the synthesizer and synthesis work of a kind of new doughnut Silicalite-1 molecular screen membranes
Skill.
The content of the invention
To solve the above problems, the 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 molecular screen membranes, it is characterised in that it includes reactor, crystalline substance
Kind liquid storage tank, air heating apparatus, casting solution surge tank, the upper and lower ends of wherein reactor connect feeding line and discharging respectively
One end of pipeline, the other end of feeding line pass through four-way connection A connection crystal seed liquid feeding line, casting solution feeding line and heat
Air feed pipeline, the other end of the pipeline that discharges by four-way connection B 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, and hot-air enters
Expects pipe line is connected with air heating apparatus, and casting solution feeding line and casting solution discharging pipeline are connected to the two of casting solution surge tank
End；Described reactor is in cylinder, has feed liquid dispersion area, feed liquid contact zone and feed liquid set area successively from top to bottom, its
If middle feed liquid contact zone by channels separated into dry contact passage, single contact passage be available for single doughnut carrier crystallization into
Film, contact vias inner walls have hydrophobic coating.The internal diameter for wherein contacting passage is 30-50mm, and the synthesizer is used for 1.2-
The crystallization film forming of the doughnut carrier of 1.8mm external diameters.
It should be noted that present invention is generally directed to the doughnut carrier of 1.2-1.8mm external diameters, and the load of various outer diameter
Body needs to configure the contact passage of different inner diameters, but is not that simple carrier external diameter is smaller, and contact channel internal diameter is with regard to smaller
Relation.But the casting film liquid hydrodynamics for contacting passage are entered according to numerous known parameters such as carrier external diameter, casting film fluid viscosities
Row is investigated, to carry out coordinating regulation parameters such as internal diameter, casting film flow quantities to maximize the quality of guarantee film.Casting solution is flowing through
During doughnut carrier surface, because rational internal diameter designs so that be adhered to the sieve particle or impurity of crystal 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
Adhesion more by force without being washed.
In addition, the inwall of contact passage is preferably provided hydrophobic coating so that the inwall after crystal seed coating step is tried one's best
Crystal seed is not remained, the crystal seed of residual will necessarily grow with carrier, reduce crystal effect.Described hydrophobic coating can select
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 there is valve V72, V74, V76 successively.
Preferably, casting solution surge tank is connected 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, there is agitating device in fresh casting film liquid storage tank, it include motor, agitating shaft and
Blade.And when kettle 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 heater, and itself and reactor
Between pipeline should try one's best shortening to avoid heat from detracting.
Preferably, casting solution discharging pipeline on there is three-way connection, its export both ends respectively with casting solution surge tank, give up
Abandon casting film liquid storage tank and connected by circulating casting solution pipeline with discarded casting solution pipeline, wherein circulation casting solution pipeline and discarded casting
Valve V77, valve V78 are provided with film liquid pipeline.
Preferably, reactor outer wall has heat-insulation layer, and separator is by stainless steel integrated molding.Heat-insulation layer is set
Purpose is to ensure crystallization temperature, likewise, it can set extra heater to ensure crystallization temperature, certainly, reactor
Inside has temperature measuring equipment.
Preferably, feed liquid contact zone both sides have fixture so that doughnut carrier is fixed in feed liquid contact zone.
It is specific as follows present invention also offers a kind of preparation method of doughnut Silicalite-1 molecular screen membranes：
A kind of method for synthesizing doughnut Silicalite-1 molecular screen membranes, it is characterised in that this method applies including crystal seed
Cover, carrier drying, carrier crystallization process；Wherein,
Described crystal seed coating step is：Silicalite-1 crystal seed liquid is delivered in crystal seed liquid storage tank, by hollow fibre
Dimension carrier is fixed in contact passage, is opened valve V71, V72, crystal seed liquid is passed sequentially through crystal seed liquid feeding line, feed pipe
Line enters in reactor, and is back to crystal seed liquid storage tank, specified coating to be achieved through discharging pipeline and crystal seed liquid discharging pipeline
After time, 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 procedure；
Described carrier drying process is：Valve V73, V74 are opened, caused hot-air leads to successively in air heating apparatus
Overfire air feeding line and feeding line enter the doughnut carrier after reactor coats to 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；
Described carrier crystallization process is：In fresh casting film liquid storage tank prepare containing silicon source, TPAOH and
The casting solution of water, inputted by valve V79 in casting solution surge tank, opening valve V75, valve V76, valve V78 makes casting solution lead to successively
Cross casting solution feeding line and feeding line enters in reactor, and enter through discharging pipeline and discarded casting solution discharging pipeline and give up
Abandon in casting film liquid storage tank, after specified washing time to be achieved, close 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
Abandon 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 far as possible.Certainly, can be with the casting solution of pollution
When meeting crystallization needs, described cleaning step can not need, so as to directly carry out crystallization so that production cost is minimum.
Preferably, the Silicalite-1 sieve particles particle diameter 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 advantages below：
1. relative to traditional molecular screen membrane reactor, molecular screen membrane reactor is divided into several for single by the present invention
The contact passage of root doughnut carrier crystallization film forming, the internal diameter of passage and the flow velocity of feed liquid are contacted by controlling so that casting
Film liquid in a manner of similar cross-flow filtration along doughnut carrier flow so that the molecular screen membrane particle in casting solution
And impurity is difficult to adhering to carrier surface so as at utmost ensure that crystallization degree.
2. need to complete crystal seed coating in different devices relative to existing hollow fiber molecular sieve, dry, crystallization
Above three step is completed by rational processing arrangement, avoids physical location by process, the present invention in same device
Movement cause the fracture of doughnut carrier, further through setting suitable container 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 skill
Art characterization result shows, is 70 DEG C in operation temperature, should when feed liquid is the ethanol/water solution system that ethanol content is 5wt.%
The separation factor ＞ 100 of film, flux ＞ 1kgh-1·m-2, with high selectivity and permeation flux.
Brief 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 passage of the reactor shown in Fig. 1.
In figure, 1：Reactor；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 passage；1-7：Heat-insulation 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：Blower fan；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.
Embodiment
The utility model is described in further detail with specific embodiment below in conjunction with the accompanying drawings：
It is further details of explanation to the present invention presently in connection with drawings and examples.The accompanying drawing is simplified schematic diagram,
Only illustrate the essential structure of the present invention in a schematic way, therefore it only shows the composition relevant with the present invention.
Fig. 1 is the synthesizer of doughnut Silicalite-1 molecular screen membranes, and it includes reactor 1, crystal seed liquid storage tank
2nd, air heating apparatus 3, casting solution surge tank 4, the wherein upper and lower ends of reactor 1 connect feeding line and discharging pipeline respectively
One end, the other end of feeding line passes through four-way connection A10-1 connection 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 B10-2 connection crystal seeds liquid discharging pipeline, casting solution discharge nozzle
Line 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, and heat is empty
Gas feeding line is connected with air heating apparatus, and casting solution feeding line and casting solution discharging pipeline are connected to casting solution surge tank
4 both ends；Reactor 1 has feed liquid dispersion area 1-1, feed liquid contact zone 1-2 and feed liquid set successively from top to bottom in cylinder
Area 1-3, if feed liquid contact zone 1-2 is separated into dry contact passage 1-6 by separator 1-5, single contact passage 1-6 be available for it is single in
The crystallization film forming of hollow fiber carrier 11, contact passage 1-6 inwalls have hydrophobic coating, and feed liquid contact zone 1-2 both sides have fixture
1-4 is so that doughnut carrier is fixed in feed liquid contact zone, and contact passage 1-6 internal diameter is 45mm, and synthesizer is used for
The crystallization film forming of the doughnut carrier of 1.8mm external diameters.
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
Upper have valve V73 7-3, blower fan 8-2 and a flowmeter F92 9-2, on casting solution feeding line successively with 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, its both ends exported is respectively with casting solution surge tank 4, discarded casting film liquid storage tank 6 by circulating casting solution pipeline and discarding
Casting solution pipeline connects, wherein being provided with valve V77 7-7, valve V78 7-8 on circulation casting solution pipeline and discarded casting solution pipeline
.Reactor outer wall has heat-insulation layer 1-7, and separator 1-5 is by stainless steel integrated molding.
The method that doughnut Silicalite-1 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）Being mixed with crystal seed liquid concentration with water is（2
wt.%）Crystal seed liquid, and add 0.5wt% hydroxypropyl cellulose 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, external diameter 1.8mm）The fixation of reactor is fixed on by soaking, after 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 reactor, and is passed 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 dryings
Valve V73, V74 are opened, caused hot-air passes sequentially through hot-air feed line line and entered in air heating apparatus
Expects pipe line enters the doughnut carrier after reactor coats to 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
Using Ludox as silicon source, TPAOH is template, with deionized water be configured to SiO2: TPAOH: H2O=
The casting solution of 1: 0.17: 120 (mol ratio), at room temperature after aging, casting solution surge tank 4 is inputted by valve V79 7-9
In.
5. carrier crystallization
Open valve V75 7-5, valve V76 7-6, valve V78 7-8 make casting solution pass sequentially through casting solution feeding line and
Feeding line enters in reactor 1, and enters discarded casting film liquid storage tank 6 through discharging pipeline and discarded casting solution discharging pipeline
In, after 20s, valve V78 7-8 are closed, open valve V77 7-7 so as to be recycled by the casting solution of crystallization, it is to be achieved
After 4h, 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 are taken out from reactor, it is multiple with deionized water rinsing, and
Oven for drying to be put into after immersion 6h standby in water.
7. performance characterization
Show by Pervaporation Technology characterization result, be 70 DEG C in operation temperature, feed liquid is that ethanol content is 5wt.%
Ethanol/water solution system when, the separation factor 110 of the film, flux 1.2kgh-1·m-2。
Highly preferred embodiment of the present invention is the foregoing is only, is not intended to limit the invention.It is all the present invention principle and
Any modification, equivalent substitution and improvements done within spirit etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of synthesizer of doughnut Silicalite-1 molecular screen membranes, it is characterised in that it includes reactor（1）, it is brilliant
Kind liquid storage tank（2）, air heating apparatus（3）, casting solution surge tank（4）, wherein reactor（1）Upper and lower ends connect respectively into
One end of expects pipe line and discharging pipeline, the other end of feeding line pass through four-way connection A（10-1）Connection crystal seed liquid feeding line,
Casting solution feeding line and hot-air feed line line, the other end for the pipeline that discharges pass through four-way connection B（10-2）Connect crystal seed liquid
Discharged pipeline, casting solution discharging pipeline and hot-air vent line, and 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 connected with air heating apparatus, and casting solution feeding line and casting solution go out
Expects pipe line is connected to casting solution surge tank（4）Both ends；Described reactor（1）In cylinder, there is material successively from top to bottom
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 passage（1-6）, single contact passage（1-6）It is available for single doughnut carrier（11）Crystallization film forming,
Contact passage（1-6）Inwall has hydrophobic coating；Wherein contact passage（1-6）Internal diameter be 30-50mm, the synthesizer is used
In the crystallization film forming of the doughnut carrier of 1.2-1.8mm external diameters.
2. device 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. device according to 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）Connect, 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）, its
The both ends of outlet respectively with casting solution surge tank（4）, discarded casting film liquid storage tank（6）By circulating casting solution pipeline and discarded casting film
Liquid pipe line connects, wherein being provided with valve V77 on circulation casting solution pipeline and discarded casting solution pipeline（7-7）, valve V78（7-8）.
5. device according to claim 1, it is characterised in that reactor outer wall has heat-insulation layer（1-7）, separator（1-5）
By stainless steel integrated molding.
6. device according to claim 1, it is characterised in that feed liquid contact zone（1-2）Both sides have fixture（1-4）With
Doughnut carrier is fixed in feed liquid contact zone.
7. a kind of method of synthesizer synthesis doughnut Silicalite-1 molecular screen membranes according to claim 4,
It is characterized in that this method includes crystal seed coating, carrier drying, carrier crystallization process；Wherein, described crystal seed coating step is：
Silicalite-1 crystal seed liquid is delivered to crystal seed liquid storage tank（2）In, doughnut carrier is fixed on contact passage（1-6）
It is interior, valve V71, V72 are opened, makes that crystal seed liquid passes sequentially through crystal seed liquid feeding line, feeding line enters in reactor, and through going out
Expects pipe line and crystal seed liquid discharging pipeline are back to crystal seed liquid storage tank, after specified coating time to be achieved, close valve V71, and
Valve V72 is closed after crystal seed liquid completely returns to crystal seed liquid storage tank and completes a crystal seed coating procedure；Described carrier is done
Dry process is：Valve V73, V74 are opened, caused hot-air passes sequentially through hot-air feed line line and entered in air heating apparatus
Expects pipe line enters the doughnut carrier after reactor coats to crystal seed and is dried, and dried hot-air passes through discharge nozzle
Line and hot-air vent line carry out emptying process, after specified drying time to be achieved, close valve V73, V74；Described
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 solution surge tank（4）In, open valve V75（7-5）, valve V76（7-6）, valve V78（7-8）Make casting solution according to
It is secondary to be entered by casting solution feeding line and feeding line in reactor, and enter through discharging pipeline and discarded casting solution discharging pipeline
Enter 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)
So as to be recycled by the casting solution of crystallization, after one section of specified crystallization time to be achieved, valve V77 is again switched off（7-7）, beat
Valve opening V78（7-8）So that casting solution enters discarded casting film liquid storage tank（6）In.
8. according to the method for claim 7, it is characterised in that prepare the Silicalite-1 sieve particle grains of crystal seed liquid
Footpath 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.
9. according to the method for claim 7, it is characterised in that washing time 20-100s, casting solution temperature be 160~
200℃；One crystallization time is 0.5~4 h；Carrier crystallization steps repeat 0~3 time.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710797610.2A CN107362695B (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of the molecular screen membranes of doughnut Silicalite 1 |
| CN201810075546.1A CN108176244A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes |
| CN201810075532.XA CN108211819A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710797610.2A CN107362695B (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of the molecular screen membranes of doughnut Silicalite 1 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810075532.XA Division CN108211819A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes |
| CN201810075546.1A Division CN108176244A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107362695A CN107362695A (en) | 2017-11-21 |
| CN107362695B true CN107362695B (en) | 2018-03-13 |
Family
ID=60311130
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710797610.2A Active CN107362695B (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of the molecular screen membranes of doughnut Silicalite 1 |
| CN201810075532.XA Withdrawn CN108211819A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes |
| CN201810075546.1A Withdrawn CN108176244A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810075532.XA Withdrawn CN108211819A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes |
| CN201810075546.1A Withdrawn CN108176244A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut Silicalite-1 molecular screen membranes |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN107362695B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007105407A1 (en) * | 2006-03-14 | 2007-09-20 | Ngk Insulators, Ltd. | Process for producing ddr type zeolite membrane |
| CN101397142A (en) * | 2007-09-24 | 2009-04-01 | 中国科学院大连化学物理研究所 | Microwave apparatus and method for synthesizing molecular sieve film |
| 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 |
-
2017
- 2017-09-06 CN CN201710797610.2A patent/CN107362695B/en active Active
- 2017-09-06 CN CN201810075532.XA patent/CN108211819A/en not_active Withdrawn
- 2017-09-06 CN CN201810075546.1A patent/CN108176244A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007105407A1 (en) * | 2006-03-14 | 2007-09-20 | Ngk Insulators, Ltd. | Process for producing ddr type zeolite membrane |
| CN101397142A (en) * | 2007-09-24 | 2009-04-01 | 中国科学院大连化学物理研究所 | Microwave apparatus and method for synthesizing molecular sieve film |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107362695A (en) | 2017-11-21 |
| CN108211819A (en) | 2018-06-29 |
| CN108176244A (en) | 2018-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107335342B (en) | A kind of synthesizer and synthetic method of doughnut type T molecular sieve film | |
| CN102166480B (en) | An apparatus and a method for synthesizing molecular sieve membranes | |
| CN106011791A (en) | Atomic layer deposition device capable of enabling powder surface to be evenly coated and method of device | |
| CN107335343B (en) | A kind of synthesizer and synthetic method of doughnut NaA molecular sieve membrane | |
| CN105073236B (en) | Ceramic separation film structure and its manufacture method | |
| CN103055716B (en) | NaA molecular sieve membrane element internal membrane preparation method | |
| CN202376991U (en) | Molecular sieve synthesis reaction kettle | |
| CN205741206U (en) | Apparatus for atomic layer deposition at powder surface uniform coated | |
| CN105056769B (en) | The preparation method and device of a kind of NaA molecular sieve membrane | |
| CN107362695B (en) | A kind of synthesizer and synthetic method of the molecular screen membranes of doughnut Silicalite 1 | |
| CN105754116A (en) | Detachable no-adhesive type emulsion granule generator | |
| CN105073640B (en) | The manufacturing method of DDR zeolite crystal and the manufacturing method of DDR zeolite film | |
| CN106139914B (en) | A kind of preparation method and device of molecular screen membrane | |
| CN109012196A (en) | The doughnut inner wall NaA type molecular sieve infiltrating and vaporizing membrane and its synthetic method dynamically synthesized in a kind of continuous current system | |
| CN205241251U (en) | Ludox closed loop reation kettle | |
| CN108264055B (en) | A kind of synthetic method of economy Silicalite-1 molecular screen membrane | |
| CN109232158A (en) | Durol continuous crystallisation process | |
| CN105895557A (en) | Substrate Processing Apparatus | |
| CN108031299A (en) | A kind of synthesizer of economy molecular screen membrane | |
| CN204973693U (en) | Chemistry strip agent apparatus for producing | |
| CN108409014A (en) | A kind of 1,3,5- trimethoxy-benzene wastewater discharge process techniques integrating absorption and evaporation | |
| CN207546519U (en) | A kind of piperonal production waste water prepares the device of white vitriol | |
| CN212369938U (en) | Film-making liquid production device of NaA molecular sieve membrane and preparation device of molecular sieve membrane | |
| CN208458414U (en) | A kind of copper sulfate crystal drying machine | |
| CN206199247U (en) | One kind industrialization drop reaction device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180211 Address after: No. 63-65, Tianhe street, Zhejiang, Wenzhou, Zhejiang Applicant after: Kong Jie Address before: 251700 Shandong city of Binzhou province Huimin County ho Fang Zhen ladder door No. 21 Licun Applicant before: Li Chenshu |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190520 Address after: 223100 North of Yandu Road and East of Hongyan Road in Hongze County Salt Chemical Zone, Huai'an City, Jiangsu Province Patentee after: Jiangsu Huang Ma Chemical Co., Ltd. Address before: 325024 No. 63-65 Zhaoping Road, Tianhe Street, Longwan District, Wenzhou City, Zhejiang Province Patentee before: Kong Jie |
|
| TR01 | Transfer of patent right |