CN106492658B - A kind of preparation method of doughnut organic gas seperation film - Google Patents
A kind of preparation method of doughnut organic gas seperation film Download PDFInfo
- Publication number
- CN106492658B CN106492658B CN201510565928.9A CN201510565928A CN106492658B CN 106492658 B CN106492658 B CN 106492658B CN 201510565928 A CN201510565928 A CN 201510565928A CN 106492658 B CN106492658 B CN 106492658B
- Authority
- CN
- China
- Prior art keywords
- film
- organic gas
- basement membrane
- preparation
- casting solution
- 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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of preparation method of doughnut organic gas seperation film, include the following steps: prepared by (1) casting solution；(2) basement membrane is handled；(3) film preparation is filled；(4) heat cross-linking；Finally obtain the doughnut organic gas seperation film that there is separation function to organic gas.A kind of preparation method of doughnut organic gas seperation film of the present invention, preparation process is easy, continuous, and the doughnut organic gas separation film strength of preparation is high, and flux is high, and resistance to pressure is good, and resistance to mass tranfer is low, and film properties are stablized；The doughnut organic gas seperation film of preparation both using interior press operation or can use outer press operation, it can be recycled in VOC, industrial tail gas processing, the fields such as organic gas mixture separation and other need the fields such as petrochemical industry, biology, medicine and the energy of high-performance organic gas seperation film to obtain good application.
Description
Technical field
The present invention relates to film preparation and technical field of membrane surface modification, and in particular to a kind of doughnut organic gas separation
The preparation method of film.
Background technique
During oil refining, chemical industry and oil storage and transportation, some organic gas are often discharged, in chemical production process
Oil gas etc. in the saturated gas of all kinds of solvents of discharge, oil depot, while causing the huge wasting of resources, also has environment
Great destruction.As being gradually increased for environmental requirement drives with energy-saving economic interests, to the height of organic gas
Effect separation, enrichment and recycling become urgent need.
Relative to separation, enrichment and the recovery method of the organic gas such as traditional catalysis burning and activated carbon adsorption, film point
From method due to having many advantages, such as cost and low energy consumption, separation is high and without secondary pollution, separated and recovered in organic gas
Field receives significant attention.
The core of UF membrane is the exploitation of high performance membrane.Membrane material is divided into glassy state and two kinds of rubbery state, (small to fixed gas
Molecular gas includes hydrogen, nitrogen, oxygen, helium etc.) preferentially through the separation of film, using glassy polymers film.For having
For the separation of machine gas, it is often desirable that the macromolecular (all kinds of alkane, alkene) that can be coagulated preferentially penetrates film.Due to rubbery feel polymer
Glass transition temperature it is low, strand shakes and persistent movement in curly, polymeric inner can be formed one it is moving logical
Road.There is similar intermiscibility simultaneously, therefore organic in organic gas between organic molecule and rubbery feel polymer macromolecule
Object molecule Preferential adsorption and is quickly spread in film, final preferentially to penetrate film.
Existing organic gas seperation film is mostly the plate membrane that organosilicon material is prepared by coating process, reported in the literature
A small number of doughnut organic gas seperation films are also all the asymmetric hollow fiber basement membranes in non-solvent induction phase inversion preparation
Surface pass through coating crosslinking preparation.Asymmetric hollow fiber base film strength is low, and membranous wall is thick, and resistance to mass tranfer is big, simultaneously
Its outer surface is dense layer surface, therefore casting solution can not enter in fenestra in coating process, insecure in conjunction with basement membrane,
Therefore the usual intensity of doughnut organic gas seperation film being prepared by this basement membrane is low, flux is small, resistance to swelling by solvent
Difference, it is often more important that, since overlay is in the outer surface of doughnut organic gas seperation film, this doughnut organic gas
Seperation film can only carry out outer press operation, cannot achieve the interior press operation for more having separation advantage.
The wall thickness of the hollow fiber polymer membrane of fusion drawn method preparation is smaller than 20 microns, and basement membrane intensity is high, and fenestra passes through
Logical, porosity is very high, and material is usually polypropylene, polyethylene, polyvinyl chloride or polytetrafluoroethylene (PTFE).The height of fusion drawn method preparation
Molecule hollow-fibre membrane is used as the basement membrane of organic gas seperation film, can be obtained good tensile strength and biggish be compared table
Area, and it is readily processible to membrane module.
Usual organic gas seperation film is prepared by film surface coating, is avoided infiltrating casting solution inside fenestra, be prevented
Plug-hole and reduce flux.And the present invention then utilizes the wellability of casting solution and basement membrane, make casting solution be filled into basement membrane fenestra it
In, it then carries out solvent volatilization and cross-linking reaction, the separating layer (functional layer) of formation is filled in inside the fenestra of basement membrane, generation is filled out
Fill the doughnut organic gas seperation film of type.Doughnut organic gas seperation film obtained in this way, separating layer and basement membrane knot
It closes closely, and separating layer thickness can be regulated and controled by casting solution concentration, while guaranteeing flux, also be obtained very high
Specific surface area and tensile strength；Importantly, the aperture due to basement membrane penetrates through, doughnut organic gas obtained point
Interior press operation can be carried out from film, this is can not achieve using doughnut organic gas seperation film prepared by other methods
's.When interior press operation, Uniform gas flow velocity is long with membranous wall time of contact, can greatly improve the effect of embrane method processing organic gas
Rate.
Summary of the invention
Low for existing doughnut organic gas separation film-strength, basement membrane wall thickness is larger, resistance to mass tranfer is high, function
Ergosphere is easy to produce disengaging Swelling coated in membrane surface and functional layer is only attached to basement membrane outer surface and cannot achieve
The problem of interior press operation, the hollow fiber polymer membrane that the present invention is prepared using fusion drawn method utilize its wellability, film as basement membrane
Hole perforation and the high feature of porosity, are filled into casting solution in the fenestra of basement membrane, the doughnut for developing filled-type has
Machine gas separation membrane realizes interior press operation while obtaining excellent permeability energy and separating property, and avoiding doughnut has
Machine gas separation membrane film wire the problem of deformation occurs in outer press operation, high-pressure membrane filtering is realized, to expand membrane process
In the application of organic gas separation field and applicable elements.
To achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of preparation method of doughnut organic gas seperation film, includes the following steps:
(1) prepared by casting solution: dimethyl silicone polymer (PDMS) and ethyl orthosilicate are added to organic solvent-normal hexane
Or among normal heptane, stirs 24 hours, form mixed solution after mixing；Add a certain amount of catalyst dibutyltin silicic acid two
Butyl tin, it is agitated to form casting solution after mixing.
(2) basement membrane is handled: selecting the hollow fiber polymer membrane of fusion drawn method preparation as basement membrane, using ethyl alcohol or just
Hexane cleans it, avoids remaining other additives or solid particle influence functional layer filling in fenestra.
(3) fill film preparation: by basement membrane 1 with certain speed drawing by knifing head 2, knifing head 2 is by casting solution by base
Blade coating makes to be formed among casting solution infiltration to the fenestra of basement membrane in basement membrane outer surface, while by adjusting film pressure is scraped on the outside of film 1
Filling film filled with casting solution.
(4) heat cross-linking: filling film is pulled into heat cross-linking device 3 by wrap-up 4, is carried out at a certain temperature
Solvent volatilization and deep-crosslinked react certain time, make to fill the casting solution crosslinking curing filled in film surface and fenestra, shape
Pairs of organic gas is with separation function and with the doughnut organic gas seperation film of separating layer.
On the basis of above scheme, dimethyl silicone polymer described in step (1) and ethyl orthosilicate are in mixed solution
In mass fraction be respectively 2~50% and 0.1~10%,
Mass percent of the catalyst in casting solution is 0.001~0.5%.
On the basis of above scheme, hollow fiber polymer membrane described in step (2) is melt spinning-pulling method
(MSCS) polypropylene, polyethylene, polyvinyl chloride or the polytetrafluoroethylhollow hollow fiber membrane being prepared, wall thickness are that 15-50 is micro-
Rice, for porosity between 20%-80%, pore diameter range is 100~2000nm.
On the basis of above scheme, knifing speed described in step (3) is 0.01~1m/min, and the film pressure of scraping is
0.001~0.2Mpa.
On the basis of above scheme, temperature described in step (4) is 20~200 DEG C, and the time is 0.1~10 small
When.
On the basis of above scheme, preferred preparation process is as follows:
(1) prepared by casting solution: dimethyl silicone polymer and ethyl orthosilicate are added in n-hexane, stirred 24 hours,
Mixed solution is formed, the mass fraction of dimethyl silicone polymer and ethyl orthosilicate in mixed solution is respectively 20% and 4%.
The catalyst dibutyltin silicic acid dibutyl tin for accounting for total mass fraction 0.05% is added into above-mentioned solution again, makes it completely by stirring
Dissolution, prepares casting solution.
(2) basement membrane handle: select wall thickness be 15 microns, porosity 80%, the fusion drawn method that average pore size is 500 nanometers
The polyethylene hollow fiber membrane of preparation is basement membrane, and basement membrane is impregnated and cleaned with n-hexane, avoids remaining it in fenestra
His additive or solid particle influence functional layer filling.
(3) film preparation is filled: as shown in Figure 1, basement membrane 1 is passed through knifing head 2, knifing with the speed drawing of 0.01m/min
First 2 scratch casting solution in basement membrane outer surface, while it is that 0.01Mpa infiltrates casting solution and is filled into basement membrane that film pressure is scraped in adjustment
Among fenestra, filling film is formed；
(4) heat cross-linking: the rolling device 4 of filling film is pulled into heat cross-linking device 3, and solvent volatilization is carried out at 65 DEG C
With deep-crosslinked 10 hours, make fill film surface casting solution crosslinking curing, formed to organic gas have separation function in
Hollow fiber organic gas seperation film.
The doughnut organic gas seperation film of above-mentioned preferred preparation process preparation is tested for the property, data are aobvious
Show, which is 23 to the separation of propane and nitrogen, and the separation to n-hexane and nitrogen is 31, nitrogen 0.1Mpa just
It presses, flux is 0.18Nm under -0.095Mpa vacuum degree3/m2h.Experiments have shown that doughnut organic gas separation of the present invention
Film gas flux with higher and separation.It is 0.003m using membrane area2Doughnut organic gas seperation film, it is right
It is small to carry out 500 for the mixed gas (Balance Air is nitrogen) for the n-hexane (concentration 1320ppm) and nitrogen that flow velocity is 60mL/min
When separating experiment, tail gas concentration is consistently lower than 80mg/m3.Experiments have shown that doughnut organic gas seperation film of the present invention
With preferable swelling resistance effect, performance is stablized.
The prior art can be used in knifing head of the present invention.
Doughnut organic gas seperation film of the present invention overcomes existing doughnut organic gas seperation film
The problems such as wall thickness is big, and resistance to mass tranfer is high, and intensity is low.Its separating layer is filled among the fenestra of basement membrane, is securely tied with basement membrane
It closes, organic gas can be handled, realize interior press operation, film wire is difficult to bear high pressure and occur when avoiding outer press operation
Deformation leads to the problem of function layer defects and falls off.This method can be by the adjustment to casting solution concentration come adjusting film simultaneously
Thickness, so that separating layer thickness is adjusted, to obtain bigger membrane flux.
A kind of preparation method of doughnut organic gas seperation film of the present invention, has the advantage that and prepared
Journey is easy, continuous, and the doughnut organic gas separation film strength of preparation is high, and flux is high, and resistance to pressure is good, and resistance to mass tranfer is low,
Film properties are stablized；
In the doughnut organic gas seperation film of preparation, the separating layer with separation function is firmly combined with basement membrane, point
Absciss layer can be effectively treated the organic gas on the outside of film inner cavity and film, using interior press operation or can both use
Outer press operation.
The doughnut organic gas seperation film prepared using the method for the invention, due to having the above excellent property
Can, can recycle in VOC, industrial tail gas processing, organic gas mixture separate etc. fields and other need high-performance organic
The fields such as petrochemical industry, biology, medicine and the energy of gas separation membrane obtain good application.
Detailed description of the invention
The present invention has following attached drawing:
Fig. 1 knifing process flow diagram
The structural schematic diagram of Fig. 2 knifing head
Fig. 3 basement membrane outer surface SEM photograph
The outer surface SEM photograph of Fig. 4 dimethyl silicone polymer concentration prepared Ho llow fiber membrane for gas separation when being 5%
The outer surface SEM photograph of Fig. 5 dimethyl silicone polymer concentration prepared Ho llow fiber membrane for gas separation when being 10%
The outer surface SEM photograph of Fig. 6 dimethyl silicone polymer concentration prepared Ho llow fiber membrane for gas separation when being 20%
The outer surface SEM photograph of Fig. 7 dimethyl silicone polymer concentration prepared Ho llow fiber membrane for gas separation when being 40%
Wherein, 1 is basement membrane；2 be knifing head；3 be heat cross-linking device；4 be wrap-up.
Specific embodiment
Below in conjunction with attached drawing, invention is further described in detail.
As shown in Figs. 1-2, a kind of preparation method of doughnut organic gas seperation film, comprises the following steps:
(1) prepared by casting solution: dimethyl silicone polymer (PDMS) and ethyl orthosilicate are added to organic solvent-normal hexane
Or among normal heptane, stirs 24 hours, form mixed solution after mixing；Add a certain amount of catalyst dibutyltin silicic acid two
Butyl tin, it is agitated to form casting solution after mixing.
(2) basement membrane is handled: selecting the hollow fiber polymer membrane of fusion drawn method preparation as basement membrane, using ethyl alcohol or just
Hexane cleans it, avoids remaining other additives or solid particle influence functional layer filling in fenestra.
(3) fill film preparation: by basement membrane 1 with certain speed drawing by knifing head 2, knifing head 2 is by casting solution by base
Blade coating makes to be formed among casting solution infiltration to the fenestra of basement membrane in basement membrane outer surface, while by adjusting film pressure is scraped on the outside of film 1
Filling film filled with casting solution.
(4) heat cross-linking: filling film is pulled into heat cross-linking device 3 by wrap-up 4, is carried out at a certain temperature
Solvent volatilization and deep-crosslinked react certain time, make to fill the casting solution crosslinking curing filled in film surface and fenestra, shape
Pairs of organic gas is with separation function and with the doughnut organic gas seperation film of separating layer.
Embodiment 1
(1) prepared by casting solution: dimethyl silicone polymer and ethyl orthosilicate are added in n-hexane, stirred 24 hours,
Mixed solution is formed after mixing, and the mass fraction of dimethyl silicone polymer and ethyl orthosilicate in mixed solution is respectively
40% and 8%.The catalyst dibutyltin silicic acid dibutyl tin for accounting for total mass fraction 0.02% is added into above-mentioned solution again, by stirring
It mixes and makes it completely dissolved, prepare casting solution.
(2) basement membrane is handled: selection wall thickness is 30 microns, porosity 50%, average pore size are 200 nanometers of fusion drawn legal systems
Standby polyethylene hollow fiber membrane is impregnated and is cleaned to basement membrane as basement membrane, with n-hexane, avoids remaining it in fenestra
His additive or solid particle influence functional layer filling.
(3) it fills film preparation: knifing head, casting solution blade coating being passed through with 0.2m/min speed as shown in Figure 1, drawing basement membrane
Filling is formed using scraping among the fenestra that film pressure penetrates through casting solution infiltration to basement membrane for 0.01Mpa in basement membrane outer surface
Film.
(4) heat cross-linking: filling film is pulled into heat cross-linking device, and solvent volatilization is carried out at 150 DEG C and depth is handed over
Connection 1 hour makes the casting solution crosslinking curing for filling film surface, and being formed has the doughnut of separation function organic organic gas
Gas separation membrane.
Doughnut organic gas seperation film is tested for the property, and data are shown, separation of the film to propane and nitrogen
Coefficient is 21.5, and the separation to n-hexane and nitrogen is 30, nitrogen flux under 0.1Mpa positive pressure, -0.09Mpa vacuum degree
For 0.057Nm3/m2h.Experiments have shown that doughnut organic gas seperation film gas flux with higher of the present invention and
Separation.It is 0.003m using membrane area2Doughnut organic gas seperation film, to flow velocity be 40mL/min n-hexane
The mixed gas (Balance Air is nitrogen) of (concentration 1320ppm) and nitrogen, carries out 400 hours separating experiments, and tail gas concentration begins
It is lower than 100mg/m eventually3.Experiments have shown that doughnut organic gas seperation film of the present invention is imitated with preferable swelling resistance
Fruit, performance are stablized.
Embodiment 2
(1) prepared by casting solution: dimethyl silicone polymer and ethyl orthosilicate being added in hexane solution, stirring 24 is small
When, mixed solution, the mass fraction of dimethyl silicone polymer and ethyl orthosilicate in mixed solution point are formed after mixing
It Wei 2% and 0.1%.The catalyst dibutyltin silicic acid dibutyl tin for accounting for total mass fraction 0.001% is added into above-mentioned solution again,
It is made it completely dissolved by stirring, prepares casting solution.
(2) basement membrane is handled: selection wall thickness is 50 microns, porosity 20%, average pore size are 100 nanometers of fusion drawn legal systems
Standby polypropylene hollow fiber membrane is applicable in n-hexane and basement membrane is impregnated and cleaned, avoid remaining in fenestra as basement membrane
Other additives or solid particle influence functional layer filling.
(3) fill film preparation: as shown in Figure 1, drawing basement membrane with 1m/min speed by knifing head, casting solution blade coating exists
Basement membrane outer surface forms filling film using scraping among the fenestra that film pressure penetrates through casting solution infiltration to basement membrane for 0.001Mpa.
(4) heat cross-linking: filling film is pulled into heat cross-linking device, and solvent volatilization and deep-crosslinked are carried out at 20 DEG C
10 hours, make the casting solution crosslinking curing for filling film surface, being formed has the doughnut of separation function organic organic gas
Gas separation membrane.
Doughnut organic gas seperation film is tested for the property, and data are shown, separation of the film to propane and nitrogen
Coefficient is 13, and the separation to n-hexane and nitrogen is 21, nitrogen flux under 0.2Mpa positive pressure, -0.095Mpa vacuum degree
For 0.136Nm3/m2h.Experiments have shown that doughnut organic gas seperation film gas flux with higher of the present invention and
Separation.It is 0.003m using membrane area2Doughnut organic gas seperation film, to flow velocity be 40mL/min n-hexane
The mixed gas (Balance Air is nitrogen) of (concentration 1320ppm) and nitrogen, carries out 400 hours separating experiments, and tail gas concentration begins
It is lower than 120mg/m eventually3.Experiments have shown that doughnut organic gas seperation film of the present invention is imitated with preferable swelling resistance
Fruit, performance are stablized.
Embodiment 3
(1) prepared by casting solution: dimethyl silicone polymer and ethyl orthosilicate being added in hexane solution, stirring 24 is small
When, mixed solution, the mass fraction of dimethyl silicone polymer and ethyl orthosilicate in mixed solution point are formed after mixing
It Wei 40% and 1%.The catalyst dibutyltin silicic acid dibutyl tin for accounting for total mass fraction 0.5%, warp is added into above-mentioned solution again
It crosses stirring to make it completely dissolved, prepares casting solution.
(2) basement membrane is handled: selection wall thickness is 20 microns, porosity 70%, average pore size are 500 nanometers of fusion drawn legal systems
Standby PVC hollow fiber membrane is applicable in n-hexane and basement membrane is impregnated and cleaned, avoid remaining in fenestra as basement membrane
There are other additives or solid particle to influence functional layer filling.
(3) fill film preparation: as shown in Figure 1, drawing basement membrane with 0.05m/min speed by knifing head, casting solution is scraped
It is coated in basement membrane outer surface, using scraping among the fenestra that film pressure penetrates through casting solution infiltration to basement membrane for 0.01Mpa, forms filling
Film.
(4) heat cross-linking: filling film is pulled into heat cross-linking device, and solvent volatilization is carried out at 100 DEG C and depth is handed over
Connection 0.1 hour makes the casting solution crosslinking curing for filling film surface, and being formed there is the doughnut of separation function to have organic gas
Machine gas separation membrane.
Doughnut organic gas seperation film is tested for the property, and data are shown, separation of the film to propane and nitrogen
Coefficient is 16, and the separation to n-hexane and nitrogen is 22, nitrogen flux under 0.2Mpa positive pressure, -0.095Mpa vacuum degree
For 0.105Nm3/m2h.Experiments have shown that doughnut organic gas seperation film gas flux with higher of the present invention and
Separation.It is 0.003m using membrane area2Doughnut organic gas seperation film, to flow velocity be 40mL/min n-hexane
The mixed gas (Balance Air is nitrogen) of (concentration 1320ppm) and nitrogen, carries out 400 hours separating experiments, and tail gas concentration begins
It is lower than 80mg/m eventually3.Experiments have shown that doughnut organic gas seperation film of the present invention has preferable swelling resistance effect,
Performance is stablized.
Embodiment 4
(1) prepared by casting solution: dimethyl silicone polymer and ethyl orthosilicate being added in hexane solution, stirring 24 is small
When, mixed solution, the mass fraction of dimethyl silicone polymer and ethyl orthosilicate in mixed solution point are formed after mixing
It Wei 10% and 5%.The catalyst dibutyltin silicic acid dibutyl tin for accounting for total mass fraction 0.1%, warp is added into above-mentioned solution again
It crosses stirring to make it completely dissolved, prepares casting solution.
(2) basement membrane is handled: selection wall thickness is 20 microns, porosity 50%, average pore size are 1000 nanometers of fusion drawn methods
The polytetrafluoroethylhollow hollow fiber membrane of preparation is impregnated and is cleaned to basement membrane as basement membrane, with n-hexane, is avoided residual in fenestra
There are other additives or solid particle to influence functional layer filling.
(3) fill film preparation: as shown in Figure 1, drawing basement membrane with 0.01m/min speed by knifing head, casting solution is scraped
It is coated in basement membrane outer surface, using scraping among the fenestra that film pressure penetrates through casting solution infiltration to basement membrane for 0.1Mpa, forms filling
Film.
(4) heat cross-linking: filling film is pulled into heat cross-linking device, and solvent volatilization is carried out at 200 DEG C and depth is handed over
Connection 3 hours makes the casting solution crosslinking curing for filling film surface, and being formed has the doughnut of separation function organic organic gas
Gas separation membrane.
Doughnut organic gas seperation film is tested for the property, and data are shown, separation of the film to propane and nitrogen
Coefficient is 18, and the separation to n-hexane and nitrogen is 25, nitrogen flux under 0.2Mpa positive pressure, -0.085Mpa vacuum degree
For 0.087Nm3/m2h.Experiments have shown that doughnut organic gas seperation film gas flux with higher of the present invention and
Separation.It is 0.003m using membrane area2Doughnut organic gas seperation film, to flow velocity be 40mL/min n-hexane
The mixed gas (Balance Air is nitrogen) of (concentration 1320ppm) and nitrogen, carries out 400 hours separating experiments, and tail gas concentration begins
It is lower than 80mg/m eventually3.Experiments have shown that doughnut organic gas seperation film of the present invention has preferable swelling resistance effect,
Performance is stablized.
Embodiment 5
(1) prepared by casting solution: dimethyl silicone polymer and ethyl orthosilicate being added in hexane solution, stirring 24 is small
When, mixed solution, the mass fraction of dimethyl silicone polymer and ethyl orthosilicate in mixed solution point are formed after mixing
It Wei 50% and 10%.The catalyst dibutyltin silicic acid dibutyl tin for accounting for total mass fraction 0.01% is added into above-mentioned solution again,
It is made it completely dissolved by stirring, prepares casting solution.
(2) basement membrane is handled: selection wall thickness is 20 microns, porosity 50%, average pore size are 2000 nanometers of fusion drawn methods
The polyethylene hollow fiber membrane of preparation is impregnated and is cleaned to basement membrane as basement membrane, with n-hexane, avoids remaining in fenestra
Other additives or solid particle influence functional layer filling.
(3) it fills film preparation: knifing head, casting solution being passed through with the speed of 0.01m/min as shown in Figure 1, drawing basement membrane
Blade coating is in basement membrane outer surface, and using scraping among the fenestra that film pressure penetrates through casting solution infiltration to basement membrane for 0.2Mpa, formation is filled out
Fill film.
(4) heat cross-linking: filling film is pulled into heat cross-linking device, and solvent volatilization and deep-crosslinked are carried out at 50 DEG C
5 hours, makes the casting solution crosslinking curing for filling film surface, form the organic gas of doughnut that there is separation function to organic gas
Body seperation film.
Doughnut organic gas seperation film is tested for the property, and data are shown, separation of the film to propane and nitrogen
Coefficient is 13, and the separation to n-hexane and nitrogen is 21, and nitrogen flux under 0.2Mpa positive pressure, -0.09Mpa vacuum degree is
0.04Nm3/m2h.Experiments have shown that doughnut organic gas seperation film of the present invention gas flux with higher and separation
Coefficient.It is 0.003m using membrane area2Doughnut organic gas seperation film, to flow velocity be 20mL/min n-hexane it is (dense
Degree be 1320ppm) and nitrogen mixed gas (Balance Air is nitrogen), carry out 500 hours separating experiments, tail gas concentration is low always
In 50mg/m3.Experiments have shown that doughnut organic gas seperation film of the present invention has preferable swelling resistance effect, performance
Stablize.
Embodiment 6
(1) prepared by casting solution: dimethyl silicone polymer and ethyl orthosilicate are added in n-hexane, stirred 24 hours,
Mixed solution is formed after mixing, and the mass fraction of dimethyl silicone polymer and ethyl orthosilicate in mixed solution is respectively
20% and 4%.The catalyst dibutyltin silicic acid dibutyl tin for accounting for total mass fraction 0.05% is added into above-mentioned solution again, by stirring
It mixes and makes it completely dissolved, prepare casting solution.
(2) basement membrane is handled: selection wall thickness is 15 microns, porosity 80%, average pore size are 500 nanometers of fusion drawn legal systems
Standby polyethylene hollow fiber membrane is basement membrane, and basement membrane is impregnated and cleaned with n-hexane, avoids remaining other in fenestra
Additive or solid particle influence functional layer filling.
(3) film preparation is filled: as shown in Figure 1, by basement membrane with the speed drawing of 0.01m/min by knifing head, by casting film
Liquid on the outside of basement membrane by scratching in basement membrane outer surface, while it is that 0.01Mpa infiltrates casting solution and is filled into base that film pressure is scraped in adjustment
Among film fenestra, filling film is formed.
(4) heat cross-linking: filling film is pulled into heat cross-linking device, and solvent volatilization and deep-crosslinked are carried out at 65 DEG C
10 hours, make the casting solution crosslinking curing for filling film surface, being formed has the doughnut of separation function organic organic gas
Gas doughnut organic gas seperation film.
Doughnut organic gas seperation film is tested for the property, and data are shown, separation of the film to propane and nitrogen
Coefficient is 23, and the separation to n-hexane and nitrogen is 31, nitrogen flux under 0.1Mpa positive pressure, -0.095Mpa vacuum degree
For 0.18Nm3/m2h.Experiments have shown that doughnut organic gas seperation film gas flux with higher of the present invention and point
From coefficient.It is 0.003m using membrane area2Doughnut organic gas seperation film, to flow velocity be 60mL/min n-hexane
The mixed gas (Balance Air is nitrogen) of (concentration 1320ppm) and nitrogen, carries out 500 hours separating experiments, and tail gas concentration begins
It is lower than 80mg/m eventually3.Experiments have shown that doughnut organic gas seperation film of the present invention has preferable swelling resistance effect,
Performance is stablized.
Casting solution concentrations control example
(1) prepared by casting solution: dimethyl silicone polymer and ethyl orthosilicate are added in normal heptane, stirred 24 hours,
Mixed solution is formed after mixing；Mass fraction of the dimethyl silicone polymer just in mixed solution be respectively 5%, 10%,
20%, 40%；Mass fraction of the silester in mixed solution is respectively 1%, 2%, 4%, 8%；Again into above-mentioned solution
Addition accounts for the catalyst dibutyltin silicic acid dibutyl tin that total mass fraction is respectively 0.025%, 0.05%, 0.1%, 0.2%, passes through
Stirring makes it completely dissolved, and prepares casting solution.
(2) basement membrane is handled: being selected average wall thickness to be 2000 nanometers less than 20 microns, porosity 45%, average pore size and is melted
The polyethylene hollow fiber membrane of pulling method preparation is basement membrane, is impregnated basement membrane 5 hours using normal heptane, avoids remaining addition in fenestra
Agent or solid particle influence functional layer filling.
(3) film preparation is filled: as shown in Figure 1, basement membrane is passed through knifing head, casting solution with the speed drawing of 0.01m/min
Blade coating is in basement membrane outer surface, while it is that 0.01Mpa infiltrates casting solution among the fenestra penetrated through to basement membrane that film pressure is scraped in adjustment, shape
At filling film.
(4) heat cross-linking: the rolling device of filling film is pulled into heat cross-linking device, and solvent volatilization is carried out at 150 DEG C
With deep-crosslinked 1 hour, make fill film surface casting solution crosslinking curing, formed to organic gas have separation function it is hollow
Fiber organic gas seperation film.
Fig. 3 is basement membrane outer surface SEM photograph, and Fig. 4-7 is that dimethyl silicone polymer concentration is respectively 5%, 10%, 20% and
The outer surface SEM photograph of prepared Ho llow fiber membrane for gas separation when 40%；
The performance of resulting doughnut organic gas seperation film is tested, the hollow fibre of four different formulations preparation
The separating layer thickness (separating layer thickness passes through Electronic Speculum and energy spectrum estimation) of organic gas seperation film is tieed up, and under 0.1Mpa pressure
Propane and nitrogen flux be shown in Table 1.
It is demonstrated experimentally that by this method can the excellent organic gas seperation film of processability, the structure and performance of the film
It can be adjusted by regulating and controlling casting solution concentration.
Under 1 0.1Mpa of table, the flux of pure nitrogen gas and pure propane flammable gas
The content being not described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.
Claims (4)
1. a kind of preparation method of doughnut organic gas seperation film, which comprises the steps of:
(1) prepared by casting solution: by dimethyl silicone polymer and ethyl orthosilicate be added to organic solvent-normal hexane or normal heptane it
In, it stirs 24 hours, forms mixed solution；A certain amount of catalyst dibutyltin silicic acid dibutyl tin is added, agitated mixing is equal
Casting solution is formed after even；
(2) basement membrane is handled: selecting the hollow fiber polymer membrane of fusion drawn method preparation as basement membrane (1), using ethyl alcohol or just
Hexane cleans it；
(3) fill film preparation: by basement membrane (1) with certain speed drawing by knifing head (2), knifing head (2) scrapes casting solution
It is coated in basement membrane outer surface, while making to be formed among casting solution infiltration to the fenestra of basement membrane filled with casting by adjusting film pressure is scraped
The filling film of film liquid；
(4) heat cross-linking: filling film is pulled into heat cross-linking device (3) by wrap-up (4), is carried out at a certain temperature
Solvent volatilization and deep-crosslinked react certain time, make to fill the casting solution crosslinking curing filled in film surface and fenestra, shape
At the doughnut organic gas seperation film with separating layer；
The mass fraction of dimethyl silicone polymer and ethyl orthosilicate in mixed solution described in step (1) is respectively 2~
50% and 0.1~10%；
Mass percent of the catalyst in casting solution described in step (1) is 0.001~0.5%；
Hollow fiber polymer membrane described in step (2) be melt spinning-pulling method be prepared polypropylene, polyethylene,
Polyvinyl chloride or polytetrafluoroethylhollow hollow fiber membrane；
The wall thickness of the hollow-fibre membrane is 15-50 microns, porosity 20%-80%, and pore diameter range is 100~2000nm；
Knifing speed described in step (3) is 0.01~1m/min；
It is 0.001~0.2Mpa that film pressure is scraped described in step (3).
2. the preparation method of doughnut organic gas seperation film as described in claim 1, which is characterized in that institute in step (4)
Stating temperature is 20~200 DEG C.
3. the preparation method of doughnut organic gas seperation film as described in claim 1, which is characterized in that institute in step (4)
Stating the time is 0.1~10 hour.
4. the preparation method of doughnut organic gas seperation film as described in claim 1, which is characterized in that including walking as follows
It is rapid:
(1) prepared by casting solution: dimethyl silicone polymer and ethyl orthosilicate being added in n-hexane, stirred 24 hours, is formed
The mass fraction of mixed solution, dimethyl silicone polymer and ethyl orthosilicate in mixed solution is respectively 20% and 4%；Again
The catalyst dibutyltin silicic acid dibutyl tin for accounting for total mass fraction 0.05% is added into above-mentioned solution, keeps it completely molten by stirring
Solution, prepares casting solution；
(2) basement membrane is handled: selecting wall thickness is 15 microns, prepared by porosity 80%, the fusion drawn method that average pore size is 500 nanometers
Polyethylene hollow fiber membrane be basement membrane (1), basement membrane is impregnated and is cleaned with n-hexane；
(3) fill film preparation: by basement membrane (1) with the speed drawing of 0.01m/min by knifing head (2), knifing head (2) is by casting film
Liquid blade coating is in basement membrane outer surface, while it is that 0.01Mpa infiltrates casting solution and is filled among basement membrane fenestra that film pressure is scraped in adjustment,
Form filling film；
(4) heat cross-linking: the rolling device of filling film (4) is pulled into heat cross-linking device (3), and solvent volatilization is carried out at 65 DEG C
With deep-crosslinked 10 hours, make fill film surface casting solution crosslinking curing, formed to organic gas have separation function in
Hollow fiber organic gas seperation film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510565928.9A CN106492658B (en) | 2015-09-08 | 2015-09-08 | A kind of preparation method of doughnut organic gas seperation film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510565928.9A CN106492658B (en) | 2015-09-08 | 2015-09-08 | A kind of preparation method of doughnut organic gas seperation film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106492658A CN106492658A (en) | 2017-03-15 |
| CN106492658B true CN106492658B (en) | 2019-02-19 |
Family
ID=58287923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510565928.9A Active CN106492658B (en) | 2015-09-08 | 2015-09-08 | A kind of preparation method of doughnut organic gas seperation film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106492658B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109745869A (en) * | 2017-11-08 | 2019-05-14 | 浙江省化工研究院有限公司 | A kind of preparation method of Ho llow fiber membrane for gas separation |
| CN108807802A (en) * | 2018-08-20 | 2018-11-13 | 湖南烁普新材料有限公司 | Highly-breathable polymer-coated diaphragm and its preparation method and application |
| WO2023160073A1 (en) * | 2022-02-23 | 2023-08-31 | 中国石油化工股份有限公司 | Hollow fiber seperation membrane, preparation method therefor and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229487A (en) * | 2007-11-06 | 2008-07-30 | 清华大学 | PDMS/PVDF complex film for separating organic steam and preparation method thereof |
| CN102284253A (en) * | 2011-06-13 | 2011-12-21 | 北京工业大学 | Method for assembling organic/inorganic hollow fiber composite membrane |
| CN103894074A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Novel hybrid membrane as well as preparation method and application thereof |
-
2015
- 2015-09-08 CN CN201510565928.9A patent/CN106492658B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229487A (en) * | 2007-11-06 | 2008-07-30 | 清华大学 | PDMS/PVDF complex film for separating organic steam and preparation method thereof |
| CN102284253A (en) * | 2011-06-13 | 2011-12-21 | 北京工业大学 | Method for assembling organic/inorganic hollow fiber composite membrane |
| CN103894074A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Novel hybrid membrane as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106492658A (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Formation of microporous polymeric membranes via thermally induced phase separation: A review | |
| CN106492658B (en) | A kind of preparation method of doughnut organic gas seperation film | |
| CN102764597B (en) | Method for preparing polyvinylidene fluoride ultra-filtration membranes | |
| US9095819B2 (en) | Composition for preparation of hollow fiber porous membrane and preparation method using the same | |
| CN101164677B (en) | Method for preparing super high molecular polythene porous membrane by thermally phase separation method | |
| CN103394297B (en) | Method for preparing hydrophilic polytetrafluoroethylene hollow fiber film | |
| CN104174303B (en) | Enhancement polyvinylidene fluoride hollow fiber ultrafiltration membrane and preparation method thereof | |
| WO2009097745A1 (en) | A polyvinylidene fluoride porous membrane and a method for producing the same | |
| CN106582314B (en) | A kind of small-bore hydrophobic composite membrane preparation method for membrane distillation | |
| CN104629151B (en) | Porous vinyl resin film with controllable structure and preparation method thereof | |
| CN103131040B (en) | Hollow microsphere of polymer having non-permeable surface, and its preparation method | |
| CN106422799A (en) | Method for preparing thin film with hierarchical hole structure by adopting double-solvent method | |
| CN106390776A (en) | Method for producing polyvinylidene fluoride porous membrane with extruder | |
| Sun et al. | Synthesis and properties of triblock copolymers containing PDMS via AGET ATRP | |
| CN109745869A (en) | A kind of preparation method of Ho llow fiber membrane for gas separation | |
| CN105461840A (en) | Preparation method of hollow pigment for papermaking coating | |
| CN1313191C (en) | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology | |
| Pan et al. | Versatile preparation of monodisperse poly (furfuryl alcohol) and carbon hollow spheres in a simple microfluidic device | |
| CN101623604A (en) | Preparation method of hollow-fiber membrane with high intensity and high flux and additive thereof | |
| CN107540863B (en) | Preparation method of totally-enclosed polymer microspheres with hollow or porous structures inside | |
| Zhang et al. | High density polyethylene-grafted-maleic anhydride low-k porous films prepared via thermally induced phase separation | |
| CN104971628A (en) | Multilayer gas separation composite membrane and preparation method thereof | |
| CN104629180A (en) | Polypropylene porous membrane and preparation method thereof | |
| CN110372900B (en) | Method for continuously preparing cellulose gel film by improved microfluidic method | |
| CN106492645A (en) | Enhancement ultra-high molecular weight polyethylene and Kynoar binary blend film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |