CN102716683A - Pervaporation hybrid membrane and application thereof - Google Patents
Pervaporation hybrid membrane and application thereof Download PDFInfo
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- CN102716683A CN102716683A CN2012102439391A CN201210243939A CN102716683A CN 102716683 A CN102716683 A CN 102716683A CN 2012102439391 A CN2012102439391 A CN 2012102439391A CN 201210243939 A CN201210243939 A CN 201210243939A CN 102716683 A CN102716683 A CN 102716683A
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Abstract
The invention discloses a pervaporation hybrid membrane and an application thereof and relates to a hybrid membrane. The invention provides a pervaporation hybrid membrane and an application thereof, wherein a polysulfone material with a benzene ring structure can ensure good mechanical properties of the membrane, the blending of a hydrophilic material and a hydrophobic material can enable the membrane to have more free volume so as to enhance the flux, and a doped metal nanometer oxide can produce conjugation effect with thiophene to increase the enrichment factor. The pervaporation hybrid membrane is a mixture of a hydrophobic polymer, a hydrophilic polymer and an inorganic metal oxide, wherein the mass fraction of the hydrophobic polymer in the mixture is less than or equal to 50%, the mass fraction of the inorganic metal oxide in the mixture is less than or equal to 10%, and the balance is the hydrophilic polymer. The pervaporation hybrid membrane can be applied in the pervaporation separation process of organic sulfur and hydrocarbon.
Description
Technical field
The present invention relates to a kind of hybridized film, especially relate to a kind of infiltration evaporation hybridized film that is used for gasoline desulfur and uses thereof.
Background technology
Catalytically cracked gasoline mainly is made up of thiophenes, alkane and cycloalkane etc. as the important component part of commercial gasoline.Thiophenes wherein belongs to the heterocyclic compound of being with sulphur atom, is the main source thing of pernicious gases such as sulfur dioxide.So, must carry out desulfurization to gasoline and handle.Along with countries in the world are to the attention further of environment in recent years, the law of restriction sulfur in gasoline content is also strict further, and the deep desulfuration of gasoline also becomes a difficult problem that needs to be resolved hurrily.
Traditional sulfur method is hydrodesulfurization, though this method can drop to arbitrarily small degree with sulfur content, its high operating cost is its unsurmountable shortcoming with causing a large amount of loss of octane number.Therefore, people attempt to research and develop the technology of some non-hydrodesulfurizations, like bacterial desulfurization, oxidation sweetening and adsorption desulfurize etc.But all there is variety of issue in the process of industrialization of these methods, makes to be difficult to carry out.With respect to these sulfur methods, the embrane method desulfurization has high efficiency, low energy consumption, is easy to advantages such as industrialization and strong adaptability, is the technology that is hopeful to replace traditional hydrodesulfurization most.Therefore, business circles and institutions for academic research have all carried out big quantity research to the infiltration evaporation desulfurization.
Infiltration evaporation (PV) utilizes the different of absorption that component passes through film and diffusion rate, by the liquid mixture component feed side with see through the side partial pressure difference and realize separating, it is a kind of new membrane separation process of researching and developing in the last thirty years.Its process is: liquid mixture flows through the feed side of film; Film see through that side vacuumizes, condensation, inert gas purge or solvent absorb and make liquid component form steam pressure difference in the both sides of film; Component sees through film under the promotion of steam pressure difference, and overflows from the side that sees through of film with the form of gas phase.Though the infiltration evaporation motive force is the steam pressure difference of component, its centrifugation does not receive the influence of component vapor liquid equilibrium.Therefore, each component molecular structure (not equal like straight chain, side chain, group position) and polarity etc. different all might become the foundation that component is separated.The selectivity of infiltration evaporation process depends on that component sees through the difference of the speed of film, and two kinds of expression modes are arranged:
1. separation factor (α) and concentration coefficient (β).
α=(y
i/y
j)/(x
i/x
j)；β=y
i/x
i
I-penetrated preferably component
Y-sees through the fluid component mole fraction; X-material liquid component mole fraction
2. permeation flux (J)
J=(Q×L)/(A×t)
Q-through liquid quality (kg); A-effective film area (m
2); T-infiltration evaporation time (h); L-film thickness (μ m)
The commercial film that is used for the infiltration evaporation desulfurization is mainly from the Grace Davison company and the ExxonMobil Research and Engineering company of the U.S..U.S. Pat 0211706 reported Grace Davison company with polyurethane-urea as the infiltration evaporation membrane material, with naphtha feed, have very high enrichment factor, but its extremely low flux makes this film can not be adapted to practical application.U.S. ExxonMobil company adopts nonionic film and ionic membrane that the gasoline desulfurization by pervaporation process is studied respectively.The nonionic film be by polyvinylpyrrolidone (PVP) or cellulose acetate (CTA) as active separating layer, the composite membrane of Kynoar (PVDF) milipore filter for supporting; Ionic membrane is a Nafion RTM film.The PVP/PVDF composite membrane can be reduced to 120ppm with the sulfur content in the material liquid of sulfur-bearing 1990ppm.The organic sulfur enrichment factor of CTA/PVDF composite membrane can reach 2.66, adopts suitable technology, can the sulfur in gasoline content of sulfur-bearing 1880ppm be reduced to 150ppm.Nafion RTM film can cement out the sour proton in the film through ion-exchange reactions through cation (like organic ion of Na+, tetraalkyl ammonium salt and quaternary alkylphosphonium salt etc.); Also can pass through organic bases processing formation organic salts such as triethanolamine, pyrimidine, thereby improve the selectivity of film sulfur-containing compound.The subject matter of the method is to need to add methyl alcohol as penetrant, has so just increased the complexity of process.
Domestic scholars has reported that also some are used for the membrane material of infiltration evaporation desulfurization.People such as the Lin of China University Of Petroleum Beijing ([2] L.Lin, G.Wang, H.Qu; J.Yang; Y.Wang, D.Shi, Y.Kong; Pervaporation performance of crosslinked polyethylene glycol membranes for deep desulfurization of FCC gasoline; Journal of Membrane Science.280 (2006) 651-658) prepared cross-linked polyethylene glycol (PEG) and be active separating layer, the PES milipore filter is the pervaporation separation that the composite membrane of supporting layer is used for true gasoline component, has obtained good effect.([3] L.Lin, Y.Kong, K.Xie such as Lin; F.Lu, R.Liu, L.Guo; S.Shao, J Yang, D Shi; Y.Zhang, Polyethylene glycol/polyurethane blend membranes for gasoline desulphurization by pervaporation technique, Separation and Purification Technology.61 (2008) 293-300) also prepared the blend film of polyurethane (PU) and PEG; Under the same terms, the pervaporation desulfurization performance of blend film is better than crosslinked PEG composite membrane.People ([4] R.Qi, C.Zhao, J.Li such as the Qi of Tsing-Hua University; Y.Wang, S.Zhu, Removal of thiophenes from n-octane/thiophene mixtures by pervaporation; Journal of Membrane Science.269 (2006) 94-100) having prepared with cross-linked dimethyl siloxane (PDMS) is active separating layer, and polyacrylonitrile (PAN) milipore filter is the composite membrane of supporting layer, and thiophene content is 500ppm in the analog gasoline component that normal octane/thiophene is formed; Temperature is in 30～70 ℃ of scopes; Flow is under the condition of 20L/h, is 3.9～4.9 to the enrichment factor of thiophene, and flux reaches 1.5-3.25kg/ (m
2H).This composite membrane is to C
6～C
8With the simulated system that thiophene is formed, under 30 ℃, permeation flux reaches 1.65kg/ (m
2H), the thiophene enrichment factor reaches 3.9.The subject matter of these membrane materials is because the mechanical performance extreme difference of material; Need do cross-linking modifiedly, and need porous support layer to give certain support, cause film-forming process complicated; And the phenomenon of peeling off that occurs separating layer and supporting layer easily can greatly influence separating effect.
Summary of the invention
The objective of the invention is to the limitation that exists in the above-mentioned background technology; Provide a kind of polysulfones material that has benzene ring structure can guarantee the good mechanical properties of film; The blend of water wetted material and hydrophobic material can make film have the more freedom volume; Thereby the raising flux, the doping of metal nano oxide can with thiophene generation conjugation, thereby improve infiltration evaporation hybridized film of enrichment factor and uses thereof.
Said infiltration evaporation hybridized film is the mixture of hydrophobic polymer, hydrophilic polymer and inorganic, metal oxide; Mass fraction≤50% of said hydrophobic polymer in mixture; Mass fraction≤10% of said inorganic, metal oxide in mixture, surplus is a hydrophilic polymer.
Optional a kind of in polysulfones (PSF), polyether sulfone (PES), polyarylsulfone (PAS) (PASF) etc. of said hydrophobic polymer.
Said inorganic, metal oxide can be selected from nano cupric oxide (CuO), nano phase ag_2 o (Ag
2O) etc. a kind of in.The particle diameter of said nano cupric oxide and nano phase ag_2 o can be less than 40nm.
Said hydrophilic polymer can be selected from a kind of in chloromethyl polysulphone (CMPSF), aminomethylation polysulfones (AMPSF), SPSF (SPS), the phenolphthalein side group polyether sulfone (PES-C) etc.
Said chloromethyl polysulphone can make through the Frideel-Carfst electrophilic substitution reaction under anhydrous condition.Said aminomethylation polysulfones can make through the Gbariel reaction under anhydrous condition.
The thickness of said infiltration evaporation hybridized film can be below the 30 μ m.
The mass fraction of said hydrophobic polymer in mixture is preferably 10%～50%, and the mass fraction of said inorganic, metal oxide in mixture is preferably 2%～10%, and surplus is a hydrophilic polymer.
Said infiltration evaporation hybridized film can be applicable to the infiltration evaporation separation process of organic sulfur and hydrocarbon.Utilize infiltration evaporation hybridized film of the present invention can separate the mixture of thiophene and alkane, alkane can be n-hexane, normal heptane, normal octane or toluene etc.
Said infiltration evaporation hybridized film is in solvent, to add hydrophilic polysulfone material and the blend of hydrophobicity polysulfones material elder generation, mixes metal oxide nanoparticles after the filtering and standing, again solution is laid on to dry on the glass plate to make.Wherein solvent can be selected from N, N-dimethylacetylamide (DMAC), and hydrophilic polymer and hydrophobic polymer blend are direct blending, need not to add crosslinking agent and additive, effectively reduce the complexity of reaction.
During preparation infiltration evaporation hybridized film, the evaporation time of solvent is controlled at 2～3h, and the evaporating temperature of baking oven is controlled at 108～112 ℃, preserves in shady and cool dry place after the film forming.
The invention has the advantages that simple in structurely, course of reaction is simple, and production cost is low, has higher mechanical properties and has higher flux and separation factor simultaneously, and application prospect is better.
Description of drawings
Fig. 1 is the scanning electron microscope diagram on infiltration evaporation hybridized film surface.In Fig. 1, scale is 500nm.
Fig. 2 is the scanning electron microscope diagram of infiltration evaporation hybridized film section.In Fig. 2, scale is 20 μ m.
Fig. 3 is the apparatus structure sketch map of preparation infiltration evaporation hybridized film.In Fig. 3, be labeled as: 1. material liquid tank, 2. peristaltic pump, 3. membrane module, 4. collecting pipe, 5. cold-trap, 6. vavuum pump.
The specific embodiment
Further specify the present invention below in conjunction with embodiment, but range of application of the present invention is not limited to following examples.
The preparation of embodiment 1 CMPSF/PSF/CuO hybridized film
Get 10g PSF and be dissolved in the 100ml carrene, add the chloromethyl ether and the 0.9g zinc chloride (catalyst) of equal in quality again, be warming up to 40 ℃ of reaction 5h.Reactant solution precipitates with excessive methanol, and deposition is with 80 ℃ of hot washes, filtration, and 70 ℃ of oven dry promptly make CMPSF.Take by weighing 1g PSF mass fraction respectively and be 10%～50% PSF and CMPSF mixture, be dissolved in respectively in the DMAC solvent that 10ml stirs, be configured to the polymer quality mark and be 5% polymer solution.Solution filters back standing and defoaming 12h, the nanometer CuO particle of 2%～10% mass fraction that mixes again, and ultrasonic concussion 10min obtains the uniform casting solution of nanoparticulate dispersed, and getting the 1mL casting solution, to be laid on area be 25cm
2The square glass plate on, glass plate places 110 ℃ of baking ovens, solvent evaporates behind the 2h, and film is taken off from glass plate, promptly obtains CMPSF/PSF/CuO infiltration evaporation hybridized film, its surface and SEM such as Fig. 1 and Fig. 2 of section.
Fig. 3 provides the apparatus structure sketch map of preparation infiltration evaporation hybridized film, and wherein, the outlet of material liquid tank 1 is connected with membrane module 3 through peristaltic pump 2; The outlet of membrane module 3 gets into cold-trap 5 through collecting pipe 4; The outlet of cold-trap 5 connects vavuum pump 6, and in addition, membrane module 3 is connected with material liquid tank 1.
The preparation of embodiment 2 AMPSF/PSF/CuO hybridized film
Take by weighing 10g CMPSF and be dissolved among the 200ml DMAC, add 8g O-phthalic base acid imide and 1.2g sodium hydride again, be heated to 85 ℃ of reaction 12h; Reactant precipitates with excessive methanol, and washing, filtration are claimed after the oven dry to go the 5g intermediate to be dissolved among the 100ml DMAC again; Add the 0.8ml hydrazine hydrate in 70 ℃ of reaction 10h; Reactant precipitates with excessive methanol, washing, filtration, and 70 ℃ of oven dry promptly obtain AMPSF.Take by weighing 1g PSF mass fraction respectively and be 10%～50% PSF and AMPSF mixture, be dissolved in respectively in the DMAC solvent that 10ml stirs, be configured to the polymer quality mark and be 5% polymer solution.Solution filters back standing and defoaming 12h, the nanometer CuO particle of 2%～10% mass fraction that mixes again, and ultrasonic concussion 10min obtains the uniform casting solution of nanoparticulate dispersed, and getting the 1mL casting solution, to be laid on area be 25cm
2The square glass plate on, glass plate places 110 ℃ of baking ovens, solvent evaporates behind the 2h, and film is taken off from glass plate, promptly obtains AMPSF/PSF/CuO infiltration evaporation hybridized film.
The preparation of embodiment 3 PES-C/PSF/CuO hybridized film
Take by weighing 1g PSF mass fraction respectively and be 10%～50% PSF and PES-C mixture, be dissolved in respectively in the DMAC solvent that 10ml stirs, be configured to the polymer quality mark and be 5% polymer solution.Solution filters back standing and defoaming 12h, the nanometer CuO particle of 2%～10% mass fraction that mixes again, and ultrasonic concussion 10min obtains the uniform casting solution of nanoparticulate dispersed, and getting the 1mL casting solution, to be laid on area be 25cm
2The square glass plate on, glass plate places 110 ℃ of baking ovens, solvent evaporates behind the 2h, and film is taken off from glass plate, promptly obtains PES-C/PSF/CuO infiltration evaporation hybridized film.
Embodiment 4 hybridized film are to the infiltration evaporation experiment of different component
Utilize the infiltration evaporation hybridized film of preparation among the embodiment 1, come sulphur component and hydrocarbon component in the separation simulation gasoline.Its separator such as Fig. 2.Table 1, table 2 and table 3 have provided the separating effect of three kinds of infiltration evaporation hybridized film of preparation among the embodiment 1 to different binary systems respectively.Film forming condition: the PSF mass fraction is 40%, and nanometer CuO mass fraction is 4%; The infiltration evaporation operating condition: the feeding liquid temperature is 40 ℃, and feed side pressure is an atmospheric pressure, and seeing through lateral pressure is 800Pa.
The separating effect of table 1 CMPSF/PSF/CuO hybridized film
The separating effect of table 2 AMPSF/PSF/CuO hybridized film
The separating effect of table 3 PES-C/PSF/CuO hybridized film
Embodiment 5 different preparation conditions are to the infiltration evaporation Effect on Performance
Utilize the infiltration evaporation hybridized film of preparation among the embodiment 1, come sulphur component and hydrocarbon component in the separation simulation gasoline.Table 4 has provided the infiltration evaporation separating effect that under the condition of different mixture ratio and different dopings, prepares the infiltration evaporation hybridized film among the embodiment 1 respectively with table 5.Data all are that the CMPSF/PSF/CuO hybridized film is separated thiophene/normal heptane two component results in the table, and operating condition: the feeding liquid temperature is 40 ℃, and feed side pressure is an atmospheric pressure, and seeing through lateral pressure is 800Pa.
The influence of table 4 different mixture comparison CMPSF/PSF/CuO hybridized film separating effect
The different CuO dopings of table 5 are to the influence of CMPSF/PSF/CuO hybridized film separating effect
Embodiment 6 different operating conditions are to the infiltration evaporation Effect on Performance
Utilize the infiltration evaporation hybridized film of preparation among the embodiment 1, come sulphur component and hydrocarbon component in the separation simulation gasoline.
Table 6 different feeds temperature is to the influence of CMPSF/PSF/CuO hybridized film separating effect
Table 7 different feeds sulfur content is to the influence of CMPSF/PSF/CuO hybridized film separating effect
Table 6 and table 7 have provided hybridized film among the embodiment 1 respectively in the influence to the infiltration evaporation separating effect of different feeds temperature and different feeds sulfur content.Being the PSF mass fraction is 40%, and nanometer CuO mass fraction is the result that 4% CMPSF/PSF/CuO hybridized film is separated thiophene/normal heptane two components.
Claims (10)
1. infiltration evaporation hybridized film; It is characterized in that mixture for hydrophobic polymer, hydrophilic polymer and inorganic, metal oxide; Mass fraction≤50% of said hydrophobic polymer in mixture; Mass fraction≤10% of said inorganic, metal oxide in mixture, surplus is a hydrophilic polymer.
2. a kind of infiltration evaporation hybridized film as claimed in claim 1; It is characterized in that the mass fraction of said hydrophobic polymer in mixture is 10%～50%; The mass fraction of said inorganic, metal oxide in mixture is 2%～10%, and surplus is a hydrophilic polymer.
3. a kind of infiltration evaporation hybridized film as claimed in claim 1 is characterized in that said hydrophobic polymer is selected from a kind of in polysulfones, polyether sulfone, the polyarylsulfone (PAS).
4. a kind of infiltration evaporation hybridized film as claimed in claim 1 is characterized in that said inorganic, metal oxide is selected from a kind of in nano cupric oxide, the nano phase ag_2 o.
5. a kind of infiltration evaporation hybridized film as claimed in claim 1, the particle diameter that it is characterized in that said nano cupric oxide and nano phase ag_2 o is less than 40nm.
6. a kind of infiltration evaporation hybridized film as claimed in claim 1 is characterized in that said hydrophilic polymer is selected from a kind of in chloromethyl polysulphone, aminomethylation polysulfones, SPSF, the phenolphthalein side group polyether sulfone.
7. a kind of infiltration evaporation hybridized film as claimed in claim 1 is characterized in that its thickness is below the 30 μ m.
8. a kind of infiltration evaporation hybridized film as claimed in claim 1 is applied to the infiltration evaporation separation process of organic sulfur and hydrocarbon.
9. a kind of infiltration evaporation hybridized film as claimed in claim 1 is applied to separate the mixture of thiophene and alkane.
10. application as claimed in claim 9 is characterized in that said alkane is n-hexane, normal heptane, normal octane or toluene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107138050A (en) * | 2017-05-27 | 2017-09-08 | 天津工业大学 | The preparation method of quaternary ammonium salt graft modification cellulose acetate reverse osmosis film |
| CN107376664A (en) * | 2017-08-09 | 2017-11-24 | 北京工业大学 | A kind of preparation method towards acid system selfreparing seperation film |
| CN108602029A (en) * | 2016-06-30 | 2018-09-28 | 环球油品公司 | Stabilization faciliated diffusion film for olefin/paraffin separation |
-
2012
- 2012-07-13 CN CN201210243939.1A patent/CN102716683B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 吴桂萍: "PES微孔膜的制备及膜反应器在废水处理中的应用研究", 《中国博士学位论文全文数据库 工程科技I辑》, no. 5, 15 May 2009 (2009-05-15) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108602029A (en) * | 2016-06-30 | 2018-09-28 | 环球油品公司 | Stabilization faciliated diffusion film for olefin/paraffin separation |
| CN108602029B (en) * | 2016-06-30 | 2021-11-16 | 环球油品公司 | Stable facilitated transfer membrane for olefin/alkane separation |
| CN107138050A (en) * | 2017-05-27 | 2017-09-08 | 天津工业大学 | The preparation method of quaternary ammonium salt graft modification cellulose acetate reverse osmosis film |
| CN107138050B (en) * | 2017-05-27 | 2020-01-14 | 天津工业大学 | Preparation method of quaternary ammonium salt grafted modified cellulose acetate reverse osmosis membrane |
| CN107376664A (en) * | 2017-08-09 | 2017-11-24 | 北京工业大学 | A kind of preparation method towards acid system selfreparing seperation film |
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