CN109433022A - A kind of preparation method of alcohol permselective membrane material - Google Patents
A kind of preparation method of alcohol permselective membrane material Download PDFInfo
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- CN109433022A CN109433022A CN201811613504.5A CN201811613504A CN109433022A CN 109433022 A CN109433022 A CN 109433022A CN 201811613504 A CN201811613504 A CN 201811613504A CN 109433022 A CN109433022 A CN 109433022A
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- zeolite
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
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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
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- 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
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
-
- 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
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- 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
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
Abstract
The invention discloses a kind of preparation methods for alcohol permselective membrane material, by the way that the zeolite granular of appropriate particle size and aggregate are mixed with carrier, and tubular type membrane material is further gone out by hydrothermal synthesis, this method can reduce crystal seed coating step in the prior art, be conducive to industrialization amplification.
Description
Technical field
It is the present invention relates to a kind of preparation method of membrane material, in particular to a kind of for alcohol saturating in industrial alcohol-water separation
The preparation method of tubular ceramic membrane.
Background technique
The organic solvent of anhydrous grade in the fields such as petrochemical industry, fine chemistry industry, medication chemistry, daily-use chemical industry and new energy
It is essential, therefore water a small amount of in organic solvent or micro is separated, so that it is above-mentioned for obtaining anhydrous grade organic solvent
Most important in field is also one of most common unit process.When the mixture of organic solvent and water reaches nearly boiling point, constant boiling point
When, due to the restriction of azeotropic balance, it cannot achieve the further separation of organic solvent and water using simple distillating method, tradition
Technique is to be separated water therein using technologies such as azeotropic distillation, extracting rectifying, compression rectification or zeolite absorption, in turn
The organic solvent of anhydrous grade is obtained, the common ground of these technologies is to require to completely vaporize material system to be drained off, is disappeared
The latent heat of phase change of consumption is huge, and high energy consumption causes operating cost high.
The infiltration evaporation membrane technology that recent decades grow up is since it is in dehydration of organic solvent, especially table in alcohol application
Reveal the low energy consumption come, do not introduce the advantages such as third component, blowdown be few, obtains the generally approval of people.And at present
Through in industrialized infiltrating and vaporizing membrane, zeolite membrane has obtained increasingly because of its regular cellular structure and good physicochemical stability
More concerns has many enterprises to carry out the research and development and industrial applications of this Zeolite-like membranes in succession successively both at home and abroad.Wherein,
For water permeable membrane, industrial applications, such as NaA zeolite membrane has been carried out, and for alcohol permselective membrane, it is not yet real
Now industrialize.For preparation Silicalite-1 zeolite membrane, common preparation method has in-situ synthesis and diauxic growth
Method, relative to in-situ synthesis, secondary growth method is higher for the crystallization process controllability of zeolite membrane, can be when relatively short
It is interior to prepare comparatively dense, smooth film layer, therefore such method is mostly used in industrial application.But use diauxic growth
Method needs to coat a layer crystal kind in advance on carrier before hydrothermal crystallizing and is then dried, therefore enters reaction kettle in carrier
It needs before carrying out hydrothermal crystallizing after the transport between crystal seed coating container and drying receptacle and multiple containers.However, for
Need together to operate more root canal formulas or doughnut carrier when industrial production, coated in the seed layer on carrier easily because
The factors such as collide with lead to seed layer rupture or even fall off, and the reduction of qualification rate is generated so as to cause film, are Zeolite-like membranes hardly possiblies
With an industrialized reason.Therefore, the new preparation method of one kind is needed to overcome secondary growth method to prepare Silicalite-1
Many disadvantages when zeolite membrane.
Summary of the invention
The present invention provides a kind of preparation methods of alcohol permselective membrane material, it is characterised in that itself the following steps are included:
(1) after mixing by alpha-alumina powder, Silicalite-1 zeolite and pore creating material, binder, after vacuum pugging
The pug of acquisition carries out extrusion forming, and carries out high-temperature roasting after the drying and obtain tubular media；
(2) casting solution is prepared by raw material of 4-propyl bromide, silica solution, potassium fluoride and water, wherein feed molar in casting solution
Than are as follows: nSiO2:nTPABr:nKF:nH2O=1:0.1-1:0.05-1:20-200；
(3) the carrier polishing treatment that will be prepared in step (1), is placed in autoclave together with casting solution and is continuously flowed
The processing of method Situ Hydrothermal is to obtain tubular type membrane material.
The innovation of the invention consists in that by as the zeolite granular of film crystallization crystal seed and the aggregate for preparing carrier and corresponding
Additive is mixed with the special carrier with revulsive crystallization film forming function.Based on the innovative point, the present invention is to aggregate
Type selected, compared in a variety of aggregates such as corundum, kaolin, mullite, Alpha-alumina, gama-alumina
The conjugation of experiment discovery, Alpha-alumina and zeolite granular is preferable.The aggregate of doping tubular media is prepared into, and in it
Portion's Situ Hydrothermal has prepared Silicalite-1 zeolite membrane.Relative to the diauxic growth using crystal seed coating, the present invention is omitted
Crystal seed applying step, is conducive to industrial method, and relative in situ synthesis, (and its internal) tool on carrier of the invention
There is zeolite granular, advantageously reduce the generated time of zeolite membrane and can effectively control the crystallization process of film, using the present invention
Carrier and synthetic method, the crystallization time of Silicalite-1 zeolite membrane be preferably 24-48h, crystallization temperature is preferably 150-
200℃。
Due to containing a certain amount of zeolite granular in carrier inside duct, if using traditional static hydrothermal synthesis method,
Casting solution is immersed always in crystallization process carrier inside, then carrier inside is also easy to grow zeolite to block carrier inside
The flux of channel reduction film.Continuous flow method Vacuum-assisted method is used thus, i.e., the both ends of tubular media is passed through into circulating pump
Be connected with synthesis liquid storage tank makes casting solution inside tubular media so that Synthesis liquid is continuously passed through with pass-out carrier, the method
It quickly continues to flow through, casting solution is avoided to immerse carrier inside to avoid carrier hole from being blocked.
Preferably, the alpha-alumina powder is spherical powder, average grain diameter 500-800nm.
Preferably, the partial size of the Silicalite-1 zeolite is 300-500nm.Preferably, the Alpha-alumina
The mass ratio of powder and the Silicalite-1 zeolite is 20:1-5:1.Likewise, for guarantee aggregate and zeolite granular it
Between combination degree, the present invention between the two particle size and content be in optimized selection, discovery work as Alpha-alumina partial size
The carrier effect prepared when 500-800nm, Silicalite-1 zeolite granular are in 300-500nm is best.
Preferably, the Silicalite-1 zeolite is to be prepared by microwave-hydrothermal method, and removed by high-temperature roasting
Template.And the Silicalite-1 zeolite granular of traditional hydrothermal synthesis method preparation is generally higher than 1.5 μm, therefore preferably uses
The Silicalite-1 particle of microwave-hydrothermal method preparation, the particle of method preparation compared to common hydro-thermal method, partial size more with
And partial size is smaller, it can be by its size controlling in 300-400nm by reasonable synthesis step.Preferred zeolite granular Synthesis liquid
Using tetrapropyl amine bromide TPABr, fumed silica, sodium hydroxide and water as raw material, wherein mol ratio is 1SiO2:
XTPABr:yN2O:zH2O, wherein x=0.1-1, y=0.05-0.3, z=30-100.Crystallization uses two crystallization methods, and the first step is brilliant
Change in 50-80 DEG C of crystallization 6-12h, then continues crystallization 8-12h between 100-150 DEG C, two crystallizations are in stirring
Lower crystallization, mixing speed 100-300rpm.It needs to indicate, microwave power uses 500-1500w here.Using microwave hydrothermal
The zeolite granular partial size of method preparation is 300-500nm, is conducive to mix with aggregate.Since synthetic zeolite uses template,
When high temperature sintering carrier, template is escaped from zeolite granular, in experiments it is found that using the zeolite system of non-removed template method
Standby carrier is easy to produce blind crack, but by the zeolite after high-temperature roasting removed template method in conjunction with aggregate when is several
There is no crackle.But in the carrier high temperature sintering stage, Silicalite-1 grain skeleton structure can still collapse, in the secure execution mode (sem
" hole " shape is presented, but uses the zeolite film surface of this method preparation opposed flattened, it may be possible to be synthesized at collapsing since particle induces
Zeolite layer it is thicker, it is relatively general so as to cause membrane flux.
Preferably, the Silicalite-1 zeolite and is passed through by the way that the zeolite of Vacuum-assisted method is carried out ball milling
It is obtained after deposition screening.It, can also be by the way of Mechanical Crushing by the Silicalite-1 of hydrothermal synthesis in addition to microwave hydrothermal
Particle (1.5 μm of average grain diameter) partial size foreshortens to the particle size range of synthesis.Traditional Mechanical Crushing mode has the side such as grinding, ball milling
Formula, preferred Mechanical Crushing mode are wet ball grinding, Ball-milling Time 2-4h, revolving speed 100-500rpm, the matter of granulation solvent
For amount than being 1:10-1:200, solvent is preferably ethyl alcohol, water.The particle of method preparation contains a large amount of amorphous substance, unfavorable
In and aggregate combination, can be used subsidence style remove amorphous substance, i.e., by ball milling suspension be placed in container stand 4h-5h,
Lower sediment thing is taken to be dried for standby, vessel level surface area is 0.01-1m2, and suspension height is 10-50cm.The preparation of this method
Zeolite granular since skeleton structure has been collapsed, carrier sintering after be not in " hole ", and collapsing zeolite granular according to
So there is induction zeolite growth ability.
Preferably, the pore creating material be carbon dust, carbon black, it is one or more in polyvinyl alcohol；The binder is stone
One of wax, dextrin and cellulose are a variety of.
Specific embodiment
For realize the present invention technological means, character of innovation, reach purpose and effect is easy to understand, below with reference to
The present invention is further described for embodiment.
Comparative example 1
(1) with microwave method synthesize Silicalite-1 zeolite, Synthesis liquid with tetrapropyl amine bromide TPABr, fumed silica,
Sodium hydroxide and water are as raw material, and wherein mol ratio is 1SiO2:0.2TPABr:0.15N2O:50H2O, and crystallization uses two steps
Then crystallization method, the first crystallization continue crystallization for 24 hours between 100 DEG C, two crystallizations are to stir in 60 DEG C of crystallization 12h
Crystallization under state, stirring rate 200rpm.After hydrothermal synthesis, by Synthesis liquid centrifugal filtration, and washing and drying, droplet measurement its
Average grain diameter is about 450nm；Continue to roast 2h removed template method under 500 DEG C of high temperature.
(2) by the Silicalite-1 zeolite of Alpha-alumina spherical powder and step (1) preparation that average grain diameter is 800nm
According to mass ratio be 10:1 mixed, and add pore creating material carbon black, binder paraffin continuess to mix uniformly, in vacuum deairing machine
The pug obtained after vacuum pugging carries out extrusion forming, and carries out high-temperature roasting after the drying and obtain tubular media, roasting temperature
Degree is 1350 DEG C.
(3) casting solution is prepared by raw material of 4-propyl bromide, silica solution, potassium fluoride and water, wherein raw material in casting solution
Molar ratio are as follows: nSiO2:nTPABr:nKF:nH2O=1:0.6:0.2:50.
(4) the carrier polishing treatment that will be prepared in step (2), and after carrier outer surface is wrapped up with Teflon adhesive tape with casting
Film liquid is placed in progress Situ Hydrothermal processing in autoclave together, and synthesis temperature is 165 DEG C, generated time 48h.
(5) after synthesizing, by reaction kettle Temperature fall, tubular type membrane material is taken out, washes with water, impregnate, dry, and
500 DEG C of Muffle kiln roasting 4h removed template methods.
Comparative example 2
(1) by homemade Silicalite-1 zeolite granular (prepared by common hydro-thermal method, 1.7 μm of partial size, removed template method) with
Ethyl alcohol is added with the mixing of 1:100 mass ratio into ball mill container, sets Ball-milling Time 3h, revolving speed 300rpm.Ball milling terminates
Ball milling liquid, which is poured into immediately in the cylindrical container that surface area is 0.1 ㎡, afterwards makes its natural subsidence, and drying after supernatant is removed after 4h
Processing, partial size test show that it is 310nm.
(2) by the Silicalite-1 zeolite of Alpha-alumina spherical powder and step (1) preparation that average grain diameter is 800nm
According to mass ratio be 10:1 mixed, and add pore creating material carbon black, binder paraffin continuess to mix uniformly, in vacuum deairing machine
The pug obtained after vacuum pugging carries out extrusion forming, and carries out high-temperature roasting after the drying and obtain tubular media, roasting temperature
Degree is 1350 DEG C.
(3) casting solution is prepared by raw material of 4-propyl bromide, silica solution, potassium fluoride and water, wherein raw material in casting solution
Molar ratio are as follows: nSiO2:nTPABr:nKF:nH2O=1:0.6:0.2:50.
(4) the carrier polishing treatment that will be prepared in step (2), and after carrier outer surface is wrapped up with Teflon adhesive tape with casting
Film liquid is placed in progress Situ Hydrothermal processing in autoclave together, and synthesis temperature is 165 DEG C, generated time 48h.
(5) after synthesizing, by reaction kettle Temperature fall, tubular type membrane material is taken out, washes with water, impregnate, dry, and
500 DEG C of Muffle kiln roasting 4h removed template methods.
Embodiment 1
(1) with microwave method synthesize Silicalite-1 zeolite, Synthesis liquid with tetrapropyl amine bromide TPABr, fumed silica,
Sodium hydroxide and water are as raw material, and wherein mol ratio is 1SiO2:0.2TPABr:0.15N2O:50H2O, and crystallization uses two steps
Then crystallization method, the first crystallization continue crystallization for 24 hours between 100 DEG C, two crystallizations are to stir in 60 DEG C of crystallization 12h
Crystallization under state, stirring rate 200rpm.After hydrothermal synthesis, by Synthesis liquid centrifugal filtration, and washing and drying, droplet measurement its
Average grain diameter is 450nm；Continue to roast 2h removed template method under 500 DEG C of high temperature.
(2) by the Silicalite-1 zeolite of Alpha-alumina spherical powder and step (1) preparation that average grain diameter is 800nm
According to mass ratio be 10:1 mixed, and add pore creating material carbon black, binder paraffin continuess to mix uniformly, in vacuum deairing machine
The pug obtained after vacuum pugging carries out extrusion forming, and carries out high-temperature roasting after the drying and obtain tubular media, roasting temperature
Degree is 1350 DEG C.
(3) casting solution is prepared by raw material of 4-propyl bromide, silica solution, potassium fluoride and water, wherein raw material in casting solution
Molar ratio are as follows: nSiO2:nTPABr:nKF:nH2O=1:0.6:0.2:50.
(4) the carrier polishing treatment that will be prepared in step (2), and carrier is fitted into dynamic autoclaved technology kettle, make tubular type
Carrier both ends are connected by pipeline with casting film liquid storage tank (having heat preservation and heating function), and circulating pump is arranged on pipeline, makes to synthesize
Liquid continuously passes in and out tubular media, setting synthesis temperature in the way of casting film liquid storage tank-circulating pump-synthesis reactor-casting film liquid storage tank
Degree is 165 DEG C, and generated time is that 48h prepares tubular type membrane material.
(5) after synthesizing, by reaction kettle Temperature fall, tubular type membrane material is taken out, washes with water, impregnate, dry, and
500 DEG C of Muffle kiln roasting 4h removed template methods.
Embodiment 2
(1) by homemade Silicalite-1 zeolite granular (prepared by common hydro-thermal method, 1.7 μm of partial size, removed template method) with
Ethyl alcohol is added with the mixing of 1:100 mass ratio into ball mill container, sets Ball-milling Time 3h, revolving speed 300rpm.Ball milling terminates
Ball milling liquid, which is poured into immediately in the cylindrical container that surface area is 0.1 ㎡, afterwards makes its natural subsidence, and drying after supernatant is removed after 4h
Processing, partial size test show that it is 310nm.
(2) by the Silicalite-1 zeolite of Alpha-alumina spherical powder and step (1) preparation that average grain diameter is 800nm
According to mass ratio be 10:1 mixed, and add pore creating material carbon black, binder paraffin continuess to mix uniformly, in vacuum deairing machine
The pug obtained after vacuum pugging carries out extrusion forming, and carries out high-temperature roasting after the drying and obtain tubular media, roasting temperature
Degree is 1350 DEG C.
(3) casting solution is prepared by raw material of 4-propyl bromide, silica solution, potassium fluoride and water, wherein raw material in casting solution
Molar ratio are as follows: nSiO2:nTPABr:nKF:nH2O=1:0.6:0.2:50.
(4) the carrier polishing treatment that will be prepared in step (2), and carrier is fitted into dynamic autoclaved technology kettle, make tubular type
Carrier both ends are connected by pipeline with casting film liquid storage tank (having heat preservation and heating function), and circulating pump is arranged on pipeline, makes to synthesize
Liquid continuously passes in and out tubular media, setting synthesis temperature in the way of casting film liquid storage tank-circulating pump-synthesis reactor-casting film liquid storage tank
Degree is 165 DEG C, and generated time is that 48h prepares tubular type membrane material.
(5) after synthesizing, by reaction kettle Temperature fall, tubular type membrane material is taken out, washes with water, impregnate, dry, and
500 DEG C of Muffle kiln roasting 4h removed template methods.
Performance test
The resulting tubular type membrane material of comparative example 1-2 and embodiment 1-2 is subjected to infiltration evaporation implementation, experimental condition is: operation temperature
60 DEG C of degree, separation system is the ethanol/water solution of 5wt.%.Acquired results are as shown in table 1.
The infiltration evaporation experimental result of tubular type membrane material synthesized by 1 embodiment 1-4 of table
The infiltration evaporation experimental result of tubular type membrane material synthesized by 1 embodiment 1-4 of table
| Sample | Selectivity | Flux (kgh-1m-2) |
| Comparative example 1 | 150 | 1.04 |
| Comparative example 2 | 141 | 1.11 |
| Embodiment 1 | 145 | 1.56 |
| Embodiment 2 | 139 | 1.61 |
As can be seen from the table, tubular type membrane material provided by the invention is used for the selective > 100, flux > of industrial alcohol-water separation
1.0 kg h-1 m-2 have preferable application value with high selectivity and permeation flux, and use continuous flow
The film poor selectivity that the film of dynamic method preparation is prepared compared to static method is away from little, but flux is increased considerably.
In addition to above preferred embodiment, there are other embodiments of the invention, and those skilled in the art can be according to this
Invention makes various changes and modifications, and as long as it does not depart from the spirit of the invention, should belong to appended claims of the present invention and determines
The range of justice.
Claims (7)
1. a kind of preparation method of alcohol permselective membrane material, it is characterised in that itself the following steps are included:
(1) after mixing by alpha-alumina powder, Silicalite-1 zeolite and pore creating material, binder, after vacuum pugging
The pug of acquisition carries out extrusion forming, and carries out high-temperature roasting after the drying and obtain tubular media；
(2) casting solution is prepared by raw material of 4-propyl bromide, silica solution, potassium fluoride and water, wherein feed molar in casting solution
Than are as follows: nSiO2:nTPABr:nKF:nH2O=1:0.1-1:0.05-1:20-200；
(3) the carrier polishing treatment that will be prepared in step (1), is placed in autoclave together with casting solution and is continuously flowed
The processing of method Situ Hydrothermal is to obtain alcohol permselective membrane material.
2. according to the method described in claim 1, it is characterized in that the alpha-alumina powder is spherical powder, average grain diameter
For 500-800nm.
3. according to the method described in claim 1, it is characterized in that the partial size of the Silicalite-1 zeolite is 300-
500nm。
4. according to the method described in claim 3, it is characterized in that the Silicalite-1 zeolite is to pass through microwave hydrothermal
Method preparation, and pass through high-temperature roasting removed template method.
5. according to the method described in claim 3, it is characterized in that the Silicalite-1 zeolite is by by water in situ
The zeolite of thermal synthesis carries out ball milling, and obtains after deposited screening.
6. according to the method described in claim 1, it is characterized in that the alpha-alumina powder and the Silicalite-
The mass ratio of 1 zeolite is 20:1-5:1.
7. according to the method described in claim 1, it is characterized in that the pore creating material is carbon dust, one in carbon black, polyvinyl alcohol
Kind is a variety of；The binder is one of paraffin, dextrin and cellulose or a variety of.
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