CN104801201B - A kind of environment-friendly preparation method thereof that infiltrating and vaporizing membrane is separated for aromatic hydrocarbons/paraffins mixture - Google Patents
A kind of environment-friendly preparation method thereof that infiltrating and vaporizing membrane is separated for aromatic hydrocarbons/paraffins mixture Download PDFInfo
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Abstract
A kind of environment-friendly preparation method thereof that infiltrating and vaporizing membrane is separated for aromatic hydrocarbons/paraffins mixture, belongs to UF membrane field.The present invention is using water as solvent, make amphipathy hyperbranched polymer molecule that micella dispersion liquid is formed in water, the particle diameter of micella is regulated and controled by the concentration for adjusting polymer, so as to match with the aperture of basement membrane, polymer micelle is deposited in the internal gutter of tubular porous ceramics basement membrane using static negative pressure method, and the structure of densification is formed it into by heat cross-linking.The method that the present invention is used does not introduce poisonous and hazardous organic solvent and crosslinking agent, with preparation process environmental protection, preparation method is simple, the advantages of low in raw material price, prepared composite membrane is used in the infiltration evaporation separation field of aromatic hydrocarbons/paraffins mixture, preferably separating property is shown, with good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of infiltrating and vaporizing membrane and its technology of preparing, a kind of specific aromatic hydrocarbons/alkane point is specifically provided
From the environment-friendly preparation method thereof of film, belong to UF membrane field.
Background technology
The separation of aromatic hydrocarbons/paraffins mixture has great importance in petrochemical industry.But due to its physicochemical property very
It is close, it is difficult to reach all the time in chemical industry efficiently separate aromatic hydrocarbons/paraffins mixture.Infiltration evaporation membrane separation technique is with it
The features such as low energy consumption, high efficiency, non-secondary pollution, it is considered as the new technology of most potential substitution conventional method.At present, it is being used for
In the infiltrating and vaporizing membrane preparation process that aromatic hydrocarbons/paraffins mixture is separate, polymer is dissolved using organic solvent generally, and adulterate
The harmful substances such as glutaraldehyde can change stretching, extension and the group of polymer molecule segment as crosslinking agent, the presence of these organic solvents
Between interaction force, influence polymeric material is to the permselective property of aromatic hydrocarbons.There is the poisonous of introducing during film preparation simultaneously
Machine waste liquid is difficult to process, and human body and air can be damaged.In film commercial Application, water is replaced as one kind is optimal
For solvent, vast potential for future development is shown.
This method selects amphipathic dissaving polymer as filmogen, can self-emulsifying shape in aqueous solvent using it
Into the characteristic of micella dispersion liquid, it is deposited onto in the duct of tubular ceramic basement membrane by static negative pressure method, forms organic/inorganic
Tubular composite membrane；It is heat-treated, reaction is crosslinked between the end group for making dissaving polymer micella, formed form compact and stable
Separating layer.Because the polar group on dissaving polymer end group has compatibility to aromatic hydrocarbons, therefore to aromatic hydrocarbons/alkane mixture
System has certain separating effect.
The present invention provide method during aromatic hydrocarbons/alkane infiltration vaporization separation film is prepared, from water as solvent, and
No added other chemical cross-linking agents, make polymer that micellar structure is formed in the form of molecule, and micella is entered base using negative pressure
Film forming in fenestra road, brings it about self-crosslinking and forms dense separation layers by heating.This method avoid toxic organic solvents pair
The potential hazard that human body and air are produced, reduces the cost investment of organic liquid waste treatment, realizes the green of film preparation process
Environmental protection.Gained composite membrane shows preferable separating effect and stability to aromatic hydrocarbons/alkane mixed system, with certain industry
Application prospect.
The content of the invention
It is an object of the invention to provide a kind of green preparation side that infiltrating and vaporizing membrane is separated for aromatic hydrocarbons/paraffins mixture
Method, in the case where separation factor is not reduced substantially, further improves flux, makes it have industrial value higher.
A kind of environment-friendly preparation method thereof that infiltrating and vaporizing membrane is separated for aromatic hydrocarbons/paraffins mixture, it is characterised in that including with
Lower step：
A) dissaving polymer is added to the water, hyperbranched polymer molecule is formed micella dispersion liquid by stirring；
B) tubular type inorganic porous membrane is pre-processed, its surface is carried functional groups；
C) the tubular type basement membrane after treatment is placed in step a) gained micella dispersion liquids, static negative pressure method deposits 1-
120min；
D) film that step c) is obtained is placed in 150 DEG C of baking ovens and is heat-treated 0.5-1h, polymer terminal group is reacted, i.e.,
Prepare composite membrane.
Described dissaving polymer is big point containing hydrophilic segment and hydrophobic segment simultaneously in the method for the invention
At least contain two kinds of functional groups of different mutually reactives, such as Boltorn W3000 on son, and end group.
Dissaving polymer described in step a) of the invention forms micella in water, and wherein dissaving polymer is dense
It is 5~15wt% to spend.
Described inorganic porous membrane is milipore filter or microfiltration membranes, the film of described inorganic porous membrane in the method for the invention
Material is Al2O3、TiO2、ZrO2And SiO2Deng the membrane aperture of described inorganic porous membrane is between 1 nanometer to 10 microns.
Being pre-processed to tubular type inorganic porous membrane described in step b) of the invention, is to immerse inorganic porous membrane
1~24h of pretreatment is carried out in silane coupler solution with amido, it is carried functional groups, rinsed and dry.
Static negative pressure method assembling film forming described in the method for the invention, is that the inorganic basement membrane of tubular type is put into hyperbranched poly
In compound micella dispersion liquid, taking out negative pressure makes micella enter into inside basement membrane duct, preferably range of negative pressure be -0.09MPa~-
0.1MPa, takes out the negative pressure time for 20min.
Prepared dissaving polymer/inorganic tubular composite membrane is used in infiltration evaporation field in the method for the invention
The separation of aromatic hydrocarbons/alkane.
Know-why of the invention：Micella dispersion liquid is formed in water using dissaving polymer, using static negative pressure method
Micella is deposited under suction function in the internal gutter of ceramic basement membrane, heat cross-linking is then carried out to it and forms composite membrane, this
The temperature and time that the combination of each technical characteristic of invention is especially heat-treated is most important to influential effect of the invention
, and the particle diameter of micella is regulated and controled by adjusting the concentration of polymer, so as to match with the aperture of basement membrane.The present invention
The method of use does not introduce poisonous and hazardous organic solvent and crosslinking agent, and with preparation process environmental protection, preparation method is simple,
The advantages of low in raw material price, prepared composite membrane is used in the infiltration evaporation separation field of aromatic hydrocarbons/paraffins mixture, table
Reveal preferably separating property, with good prospects for commercial application.
The micella dispersion liquid that the present invention is first formed polymer in water is applied to aromatic hydrocarbons/alkane infiltration vaporization separation film
Preparation in, there is provided a kind of environmental protection, simple preparation method.While polymer micelle is assembled in from negative pressure method is taken out
In substrate duct, and composite membrane is formed through heat cross-linking.Using the method for the present invention, film thickness is reduced, effectively increase film and ooze
Saturating flux, and separation factor will not be reduced.
Brief description of the drawings
Fig. 1 is that the transmission electron microscope of the dissaving polymer micella of formation in water is characterized.
The SEM of Fig. 2 composite film surfaces of the present invention is characterized.
The SEM of Fig. 3 composite membrane sections of the present invention is characterized.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
The dissaving polymer for using is the Boltorn W3000 of Perstorp companies, and tubular type inorganic porous membrane is oxidation
Aluminium milipore filter, membrane area is 26cm2。
Compound membrane preparation method：
(1) W3000 is added to the water, under magnetic agitation effect, makes W3000 that micella dispersion liquid is formed in water, it is dense
It is 5wt% to spend；
(2) tubular type inoranic membrane is pre-processed：By the second of inoranic membrane immersion 0.8wt%3- amino-triethoxysilane
2h in alcoholic solution, is put into 110 DEG C of baking oven high temperature treatment 2h after taking-up；
(3) film after treatment is placed in the solution of step (1) preparation, static state takes out negative pressure 20min, pressure for-
0.09MPa；
(4) it is placed in 150 DEG C of baking ovens after taking-up tubular membrane and is heat-treated 1h, that is, prepares composite membrane；
The composite membrane of above-mentioned preparation is carried out into infiltration evaporation performance test in infiltration evaporation membrane cisterna, test condition is：It is former
Liquid material toluene level is the toluene/n-heptane system of 50wt%, 40 DEG C of experimental temperature, film downstream lateral pressure 800Pa.
Measuring infiltration evaporation film properties is：Permeation flux 311.4g/ (m2H), toluene level is 75.5% in permeate, point
It is 3.1 from the factor.
Embodiment 2
The dissaving polymer for using is the Boltorn W3000 of Perstorp companies, and tubular type inorganic porous membrane is oxidation
Aluminium milipore filter, membrane area is 26cm2。
Compound membrane preparation method：
(1) W3000 is added to the water, under magnetic agitation effect, makes W3000 that micella dispersion liquid is formed in water, it is dense
It is 15wt% to spend；
(2) inorganic tubular membrane is pre-processed：By the second of inoranic membrane immersion 0.8wt%3- amino-triethoxysilane
2h in alcoholic solution, is put into 110 DEG C of baking oven high temperature treatment 2h after taking-up；
(3) film after treatment is placed in the solution of step (1) preparation, static state takes out negative pressure 20min, pressure for-
0.09MPa；
(4) it is placed in 150 DEG C of baking ovens after taking-up tubular membrane and is heat-treated 1h, that is, prepares composite membrane；
The polymer multilayer film of above-mentioned preparation is carried out into infiltration evaporation performance test, test condition in infiltration evaporation membrane cisterna
For：Stoste material toluene level is the toluene/n-heptane system of 50wt%, 40 DEG C of experimental temperature, film downstream lateral pressure 800Pa.
Measuring infiltration evaporation film properties is：Permeation flux 238.5g/ (m2H), toluene level is 80.5% in permeate, point
It is 4.1 from the factor.
Embodiment 3
The dissaving polymer for using is the Boltorn W3000 of Perstorp companies, and tubular type inorganic porous membrane is oxidation
Aluminium milipore filter, membrane area is 26cm2。
Compound membrane preparation method：
(1) W3000 is added to the water, under magnetic agitation effect, makes W3000 that micella dispersion liquid is formed in water, it is dense
It is 15wt% to spend；
(2) inorganic tubular membrane is pre-processed：By the second of inoranic membrane immersion 0.8wt%3- amino-triethoxysilane
2h in alcoholic solution, is put into 110 DEG C of baking oven high temperature treatment 2h after taking-up；
(3) film after treatment is placed in the solution of step (1) preparation, static state takes out negative pressure 20min, pressure for-
0.09MPa；
(4) it is placed in 150 DEG C of baking ovens after taking-up tubular membrane and is heat-treated 0.5h, that is, prepares composite membrane；
The polymer multilayer film of above-mentioned preparation is carried out into infiltration evaporation performance test, test condition in infiltration evaporation membrane cisterna
For：Stoste material toluene level is the toluene/n-heptane system of 50wt%, 40 DEG C of experimental temperature, film downstream lateral pressure 800Pa.
Measuring infiltration evaporation film properties is：Permeation flux 292.7g/ (m2H), toluene level is 77.8% in permeate, point
It is 3.5 from the factor.
Comparative example 1
The dissaving polymer for using is the Boltorn W3000 of Perstorp companies, and tubular type inorganic porous membrane is oxidation
Aluminium milipore filter, membrane area is 26cm2。
Compound membrane preparation method：
(1) W3000 is added to the water, under magnetic agitation effect, makes W3000 that micella is formed in water, concentration is
15wt%；
(2) inorganic tubular membrane is pre-processed：By the second of inoranic membrane immersion 0.8wt%3- amino-triethoxysilane
2h in alcoholic solution, is put into 110 DEG C of baking oven high temperature treatment 2h after taking-up；
(3) film after treatment is placed in the solution of step (1) preparation, static state takes out negative pressure 20min, pressure for-
0.09MPa；
(4) it is placed in 180 DEG C of baking ovens after taking-up tubular membrane and is heat-treated 1h, that is, prepares composite membrane；
The polymer multilayer film of above-mentioned preparation is carried out into infiltration evaporation performance test, test condition in infiltration evaporation membrane cisterna
For：Stoste material toluene level is the toluene/n-heptane system of 50wt%, 40 DEG C of experimental temperature, film downstream lateral pressure 800Pa.
Measuring infiltration evaporation film properties is：Permeation flux 42.3g/ (m2H), toluene level is 75.2% in permeate, point
It is 3.0 from the factor.
Comparative example 2
The dissaving polymer for using is the Boltorn W3000 of Perstorp companies, and tubular type inorganic porous membrane is oxidation
Aluminium milipore filter, membrane area is 26cm2。
Compound membrane preparation method：
(1) W3000 is added to the water, under magnetic agitation effect, makes W3000 that micella is formed in water, concentration is
15wt%；
(2) inorganic tubular membrane is pre-processed：By the second of inoranic membrane immersion 0.8wt%3- amino-triethoxysilane
2h in alcoholic solution, is put into 110 DEG C of baking oven high temperature treatment 2h after taking-up；
(3) film after treatment is placed in the solution of step (1) preparation, static state takes out negative pressure 20min；
(4) it is placed in 150 DEG C of baking ovens after taking-up tubular membrane and is heat-treated 1.5h, that is, prepares composite membrane；
The polymer multilayer film of above-mentioned preparation is carried out into infiltration evaporation performance test, test condition in infiltration evaporation membrane cisterna
For：Stoste material toluene level is the toluene/n-heptane system of 50wt%, 40 DEG C of experimental temperature, film downstream lateral pressure 800Pa.
Measuring infiltration evaporation film properties is：Permeation flux 34.6g/ (m2H), toluene level is 81.6% in permeate, point
It is 4.4 from the factor.
Comparative example 3
The dissaving polymer for using is the Boltorn W3000 of Perstorp companies, and tubular type inorganic porous membrane is oxidation
Aluminium milipore filter, membrane area is 26cm2。
Compound membrane preparation method：
(1) W3000 is added to the water, under magnetic agitation effect, makes W3000 that micella is formed in water, concentration is
15wt%；
(2) inorganic tubular membrane is pre-processed：By the second of inoranic membrane immersion 0.8wt%3- amino-triethoxysilane
2h in alcoholic solution, is put into 110 DEG C of baking oven high temperature treatment 2h after taking-up；
(3) film after treatment is placed in the solution of step (1) preparation, static state takes out negative pressure 20min, pressure for-
0.09MPa；
(4) it is placed in 150 DEG C of baking ovens after taking-up tubular membrane and is heat-treated 2.5h, that is, prepares composite membrane；
The polymer multilayer film of above-mentioned preparation is carried out into infiltration evaporation performance test, test condition in infiltration evaporation membrane cisterna
For：Stoste material toluene level is the toluene/n-heptane system of 50wt%, 40 DEG C of experimental temperature, film downstream lateral pressure 800Pa.
Measuring infiltration evaporation film properties is：Permeation flux 18.0g/ (m2H), toluene level is 85.8% in permeate, point
It is 6.0 from the factor.
Claims (4)
1. a kind of application of film, infiltration evaporation is separated for aromatic hydrocarbons/paraffins mixture, and the preparation method of film includes following step
Suddenly：
A) dissaving polymer is added to the water, hyperbranched polymer molecule is formed micella dispersion liquid by stirring；
B) tubular type inorganic porous membrane is pre-processed, its surface is carried functional groups；
C) the tubular type basement membrane after treatment is placed in step a) gained micella dispersion liquids, static negative pressure method deposits 1-120min；
D) film that step c) is obtained is placed in 150 DEG C of baking ovens and is heat-treated 0.5-1h, polymer terminal group is reacted, that is, prepared
Obtain composite membrane.
2. according to the application of the film described in claim 1, it is characterised in that described inorganic porous membrane is milipore filter or micro-filtration
Film, the membrane material of described inorganic porous membrane is Al2O3、TiO2、ZrO2Or SiO2, the membrane aperture of described inorganic porous membrane is 1
Nanometer is between 10 microns.
3. according to the application of the film described in claim 1, it is characterised in that the dissaving polymer described in step a) is in water
Middle formation micella, wherein dissaving polymer concentration are 5~15wt%.
4. according to the application of the film described in claim 1, it is characterised in that range of negative pressure is -0.09MPa~-0.1MPa, is taken out
Negative pressure 20min.
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Citations (3)
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|---|---|---|---|---|
| CN103263858A (en) * | 2013-05-15 | 2013-08-28 | 北京工业大学 | Cross-linking hyperbranched polymer composite nano filtration membrane prepared by one step method in water phase, preparation method and application |
| CN103331109A (en) * | 2013-07-16 | 2013-10-02 | 长春工业大学 | Preparation method of hyperbranched polyester-polyvinyl alcohol pervaporation membrane |
| CN104069745A (en) * | 2014-07-16 | 2014-10-01 | 北京工业大学 | Arene/alkane separated self-crosslinking hyperbranched polymer-inorganic tubular composite membrane and preparation method |
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| EP2471592A4 (en) * | 2009-08-26 | 2014-07-30 | Ibiden Co Ltd | Gas separation membrane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263858A (en) * | 2013-05-15 | 2013-08-28 | 北京工业大学 | Cross-linking hyperbranched polymer composite nano filtration membrane prepared by one step method in water phase, preparation method and application |
| CN103331109A (en) * | 2013-07-16 | 2013-10-02 | 长春工业大学 | Preparation method of hyperbranched polyester-polyvinyl alcohol pervaporation membrane |
| CN104069745A (en) * | 2014-07-16 | 2014-10-01 | 北京工业大学 | Arene/alkane separated self-crosslinking hyperbranched polymer-inorganic tubular composite membrane and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| Highly stable"pore-filling"tubular composite membrane by self-crosslinkable hyperbranched polymers for toluene/n-heptane separation;Naixin Wang, et al;《Journal of Membrane Science》;20141014;第474卷;第263-272页 * |
| One-step self-assembly fabrication of amphiphilic hyperbranched polymer composite membrane from aqueous emulsion for dye desalination;Lin Wang,et al;《Journal of Membrane Science》;20131029;第452卷;第143-151页 * |
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