CN103752182B - Ethyl cellulose permeable vaporized gasoline desulphurization membrane and preparation method thereof - Google Patents
Ethyl cellulose permeable vaporized gasoline desulphurization membrane and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to material processing field, particularly, relate to a kind of ethyl cellulose permeable vaporized gasoline desulphurization membrane and preparation method thereof. Ethyl cellulose permeable vaporized gasoline desulphurization membrane, is composited by active layer and counterdie, and active layer is the ethyl cellulose of doping C60, and counterdie is polyvinylidene fluoride film; Active layer film makes ethyl cellulose complex film for gasoline desulfurization by pervaporation on counterdie. The present invention has the gasoline component that following beneficial effect: C60 can be higher with cloud density and carries out electric charge Transfer Complexation, shows compared with large electron affinity and is suitable for desulfurization; The ethyl cellulose composite membrane of doping C60 has higher permeation flux and selective to gasoline component, thereby effectively improves separating property; After solvent annealing in process, C60 cluster electron affinity energy increases, and the infiltration rate of analog gasoline component in film increases, and permeation flux increases.
Description
Technical field
The invention belongs to material processing field, particularly, relate to a kind of ethyl cellulose permeable vaporized gasoline desulphurization membrane and preparation method thereof, utilize ethyl cellulose and C60Hydridization blending and modifying is prepared complex film for gasoline desulfurization.
Background technology
The contained organic sulfur of vehicle fuel oil is one of main pollution sources, reduce atmosphere pollution, produces clean gasoline, and the sulfur content lowering in gasoline is a key. Along with the pay attention to day by day of countries in the world to environmental protection and the increasingly stringent of environmental regulation, production low-sulfur even sweet gasoline has become a kind of development trend.
External gasoline is generally from techniques such as fluid catalytic cracking (fluidcatalyticcracking, FCC) (34%), catalytic reforming (33%), alkylation, isomerization and etherificates (approximately 33%); And the gasoline of China approximately 80% carrys out catalytic cracking, because 85%～95% sulphur in gasoline is from catalytically cracked gasoline, this makes the sulfur content in gasoline product more much larger than external gasoline. Therefore the key that reduces product gasoline sulfur content is to reduce the sulfur content of catalytically cracked gasoline. Sulfide existence form in China FCC gasoline is taking these four kinds of organic sulfur compounds of mercaptan, thioether, disulphide and thiophene-based as main, wherein the mass concentration of thiophene sulphur accounts for the more than 60% of total sulfur mass concentration, and the mass concentration of thioether sulphur and thiophenic sulfur accounts for the more than 85% of total sulfur. Therefore, the desulfur technology of catalytic gasoline and process exploitation are mainly to remove this two classes organic sulfur as main.
At present, industrial technology maturation be hydrodesulfurization, and hydrodesulfurization meeting reduce octane number. Pervaporation membrane desulfurization is to utilize fine and close high-polymer membrane gasoline component to be dissolved to the difference of diffusion, realizes a kind of membrane process that sulfide removes. Have loss of octane number less, investment cost is low, component design simply, easily operation, do not need high temperature, high pressure, the advantages such as cleanliness without any pollution, are the very competitive non-hydrogasoline desulfur technologies of one.
By the system of selection of membrane material solubility parameter, current permeable vaporized gasoline desulphurization membrane material used mostly is dimethyl silicone polymer (PDMS), polyimides (PI), polyvinylpyrrolidone (PVP), polyureas/ammonia ester (PUU) and hybrid organic-inorganic film etc. The advantages such as it is heat-resisting, corrosion-resistant, anti-oxidant that PDMS has, but its intensity is low; PI contains rigidity aromatic ring structure, and under normal temperature, in glassy state, chemical stability and mechanical property are good; PVP has hydrophily, and good solvent is many, has strong expansion character and the complexing power with many kinds of substance. But PI fine solvent is few, PVP segment compliance is poor, the surperficial easy formation crackle of film. PUU is synthetic more difficult, film forming condition harshness. Therefore these 3 kinds of polymer are all difficult for masking, and application is subject to certain limitation. Ethyl cellulose is a kind of application polymer film sulfur removal material more widely, has the advantages such as high selectivity after having sufficient resource, relatively cheap price, simple filming technology, good filming performance and film forming.
Summary of the invention
For overcoming the defect of prior art, the invention provides a kind of doping C60Improve ethyl cellulose complex film for gasoline desulfurization by pervaporation with low cost of separating property and preparation method thereof.
For achieving the above object, the present invention adopts following proposal:
Ethyl cellulose permeable vaporized gasoline desulphurization membrane, is composited by active layer and counterdie, and active layer is doping C60Ethyl cellulose, its thickness is 30-50 μ m; Counterdie is Kynoar (PVDF) film, and the thickness of counterdie is 90-110 μ m, and Kynoar (PVDF) film has stronger hydrophobic performance, is the desirable supporter of osmosis vaporizing compound membrane material; Active layer film makes ethyl cellulose complex film for gasoline desulfurization by pervaporation on counterdie.
The preparation method of above-mentioned ethyl cellulose permeable vaporized gasoline desulphurization membrane, comprises the following steps:
(1) Kynoar, Macrogol 2000,1-METHYLPYRROLIDONE are stirred 24 hours for 1:0.1-0.5:6-10 puts into 50 DEG C of waters bath with thermostatic control of round-bottomed flask in mass ratio, solution is glassy yellow, then carries out press filtration, degassed; Knifing on nonwoven, immerses in deionized water two days, puts into oven drying, obtains the polyvinylidene fluoride film that thickness is 90-110 μ m, and polyvinylidene fluoride film is the counterdie of ethyl cellulose infiltrating and vaporizing membrane;
(2) ethyl cellulose is for subsequent use after 40-60 DEG C of oven drying;
(3) by C60Join in solvent benzol C60With the mass ratio of solvent benzol be 1:1000-1500, magnetic agitation 12h, is mixed with solution;
(4) ethyl cellulose of being prepared by step (2) and crosslinking agent, initator in mass ratio 1:0.2-0.4:0.05-0.1 join in solution prepared by step (3), and magnetic agitation 12h makes casting solution;
Wherein C in ethyl cellulose and step (3)60Mass ratio be 1:0.005, crosslinking agent is 1,6-hexanediyl ester, initator is benzophenone;
(5) casting solution in step (4) is filtered with 300 object copper mesh;
(6) casting solution step (5) being filtered leaves standstill two days to remove bubble;
(7) by the degassed casting solution film of step (6) gained on Kynoar counterdie;
(8) the UV-crosslinked 40min of composite membrane step (7) being obtained;
(9) composite membrane step (8) being obtained is put into deionized water and is carried out exchange of solvent, and obtaining active layer thickness is the ethyl cellulose infiltrating and vaporizing membrane of 30-50 μ m.
In order further to improve the separating property of ethyl cellulose permeable vaporized gasoline desulphurization membrane, preferably, composite membrane step (7) being obtained is placed at 60 DEG C of solvent vapo(u)r constant temperature 1h to carry out solvent annealing in process and carries out the UV-crosslinked of step (8) again.
With respect to prior art, the present invention has following beneficial effect:
1、C60Gasoline component that can be higher with cloud density carries out electric charge Transfer Complexation, shows compared with large electron affinity and is suitable for desulfurization.
2, doping C60Ethyl cellulose composite membrane gasoline component is had to higher permeation flux and selective, thereby effectively improve separating property.
3, after solvent annealing in process, C60Cluster electron affinity energy increases, and the infiltration rate of analog gasoline component in film increases, and permeation flux increases.
Brief description of the drawings
Fig. 1 is the structure chart of ethyl cellulose complex film for gasoline desulfurization by pervaporation; Upper layer film is doping C60Ethyl cellulose, C60Molecule moves, and assembles and forms cluster; Lower floor is polyvinylidene fluoride film, and because the exchange of top layer solvent and water is very fast, the hole of formation is less, and the Kong Ze that nexine forms is larger, and Kynoar counterdie is milipore filter.
Fig. 2 is the separating property figure of embodiment 1 composite membrane, transverse and longitudinal be designated as operating temperature (DEG C), ordinate be respectively film properties evaluate two parameters: permeation flux (kg/ (m2) and sulfur enrichment factor h). Wherein curve be modification ethyl cellulose composite membrane permeation flux with operating temperature variation relation figure, another curve is that modification ethyl cellulose composite membrane sulfur enrichment factor is with operating temperature variation relation figure.
Detailed description of the invention
Embodiment mono-,
The preparation method of ethyl cellulose permeable vaporized gasoline desulphurization membrane, comprises the following steps:
(1) 60g Kynoar, 9.23g Macrogol 2000,392.3mLN-methyl pyrrolidone are put into 50 DEG C of waters bath with thermostatic control of round-bottomed flask and stirred 24 hours, solution is glassy yellow, then carries out press filtration, degassed. Use knifing machine knifing on nonwoven, the thickness of adjusting scraper is 300 μ m, and the film of scraping is immersed in deionized water two days, puts into oven drying, obtains the polyvinylidene fluoride film of 90-110 μ m, i.e. counterdie;
(2) ethyl cellulose is for subsequent use after 40-60 DEG C of oven drying;
(3) by 0.04gC60Join in 60.68mL solvent benzol, magnetic agitation 12h, is mixed with solution;
(4) take ethyl cellulose 8g and the crosslinking agent (1 in step (2), 6-hexanediyl ester) 1.727g, initator (benzophenone) 0.432g join in solution prepared by step (3), and magnetic agitation 12h makes casting solution;
(5) casting solution in step (4) is filtered with 300 object copper mesh;
(6) casting solution step (5) being filtered leaves standstill two days to remove bubble;
(7) the degassed casting solution of step (6) gained is poured on polyvinylidene fluoride film, has the even knifing of glass bar of copper wire with cover, obtain the ethyl cellulose composite membrane of 30-50 μ m;
(8) by the UV-crosslinked 40min of ethyl cellulose composite membrane complete step (7) solvent evaporates;
(9) composite membrane step (8) being obtained is put into deionized water and is carried out exchange of solvent, obtains ethyl cellulose permeable vaporized gasoline desulphurization membrane.
Ethyl cellulose permeable vaporized gasoline desulphurization membrane prepared by said method, as shown in Figure 1, is composited by active layer 1 and counterdie 2, and active layer is doping C60Ethyl cellulose, thickness is 30-50 μ m; Counterdie is Kynoar (PVDF) film, and the thickness of counterdie is 90-110 μ m, and Kynoar (PVDF) film has stronger hydrophobic performance, is the desirable supporter of osmosis vaporizing compound membrane material; Active layer film makes ethyl cellulose complex film for gasoline desulfurization by pervaporation on counterdie.
The ethyl cellulose that is counterdie at Kynoar mutually in, C60Cluster distribution uniform, Stability Analysis of Structures, makes film have better dissolving adsorptivity to thiophene.
The evaluation of the separating property of composite membrane is undertaken by infiltration evaporation device and microcoulomb, taking thiophene, toluene, cyclohexene, cyclohexane, normal heptane by volume as 1:300-400:400-500:100-200:750-850 is mixed with the analog gasoline of sulfur content as 300 μ g/g left and right. When 75 DEG C of temperature, permeation flux is 2.32, and sulfur enrichment factor is 4.72.
The separating property of prepared film within the scope of 65～85 DEG C the results are shown in Figure 2.
Embodiment bis-,
Be with the difference of embodiment mono-: the composite membrane that step (7) is obtained is placed at 60 DEG C of solvent vapo(u)r constant temperature 1h to carry out solvent annealing in process and carry out the UV-crosslinked of step (8) again; The solvent adopting is thiophene.
The evaluation of the separating property of composite membrane is with example 1, the separating property the best in the time of 75 DEG C. Permeation flux is 4.08, and sulfur enrichment factor is 4.30.
Embodiment tri-,
Be with the difference of embodiment mono-: the composite membrane that step (7) is obtained is placed at 60 DEG C of solvent vapo(u)r constant temperature 1h to carry out solvent annealing in process and carry out the UV-crosslinked of step (8) again; The solvent adopting is benzene.
The evaluation of the separating property of composite membrane is with example 1, the separating property the best in the time of 75 DEG C. Permeation flux is 4.85, and sulfur enrichment factor is 4.35.
Embodiment tetra-,
Be with the difference of embodiment mono-: the composite membrane that step (7) is obtained is placed at 60 DEG C of solvent vapo(u)r constant temperature 1h to carry out solvent annealing in process and carry out the UV-crosslinked of step (8) again; The solvent adopting is cyclohexene.
The evaluation of the separating property of composite membrane is with example 1, the separating property the best in the time of 75 DEG C. Permeation flux is 5.93, and sulfur enrichment factor is 4.55.
Embodiment five,
Be with the difference of embodiment mono-: the composite membrane that step (7) is obtained is placed at 60 DEG C of solvent vapo(u)r constant temperature 1h to carry out solvent annealing in process and carry out the UV-crosslinked of step (8) again; The solvent adopting is cyclohexane.
The evaluation of the separating property of composite membrane is with example 1, the separating property the best in the time of 75 DEG C. Permeation flux is 5.17, and sulfur enrichment factor is 4.51.
Embodiment six,
Be with the difference of embodiment mono-: the composite membrane that step (7) is obtained is placed at 60 DEG C of solvent vapo(u)r constant temperature 1h to carry out solvent annealing in process and carry out the UV-crosslinked of step (8) again; The solvent adopting is normal heptane.
The evaluation of the separating property of composite membrane is with example 1, the separating property the best in the time of 75 DEG C. Permeation flux is 3.41, and sulfur enrichment factor is 4.53.
Claims (4)
1. a preparation method for ethyl cellulose permeable vaporized gasoline desulphurization membrane, described ethyl cellulosePermeable vaporized gasoline desulphurization membrane is composited by active layer and counterdie, and active layer is doping C60Ethyl celluloseElement film, counterdie is polyvinylidene fluoride film; Active layer film makes ethyl cellulose infiltration evaporation vapour on counterdieOil desulfurization composite membrane; Active layer thickness is 30-50 μ m; The thickness of counterdie is 90-110 μ m; Its feature existsIn, step is as follows:
(1) by Kynoar, Macrogol 2000,1-METHYLPYRROLIDONE be in mass ratio1:0.1-0.5:6-10 puts into 50 DEG C of waters bath with thermostatic control of round-bottomed flask and stirs 24 hours, and solution is glassy yellow,Then carry out press filtration, degassed; Knifing on nonwoven, immerses in deionized water two days, puts into oven drying,Obtain the polyvinylidene fluoride film that thickness is 90-110 μ m, polyvinylidene fluoride film is ethyl cellulose infiltration evaporationThe counterdie of film;
(2) ethyl cellulose is for subsequent use after 40-60 DEG C of oven drying;
(3) by C60Join in solvent benzol C60With the mass ratio of solvent benzol be 1:1000-1500, magnetic forceStir 12h, be mixed with solution;
(4) ethyl cellulose of being prepared by step (2) and crosslinking agent, initator are in mass ratio1:0.2-0.4:0.05-0.1 in solution prepared by the step of joining (3), magnetic agitation 12h makes casting solution;
Wherein C in ethyl cellulose and step (3)60Mass ratio be 1:0.005, crosslinking agent be 1,6-oneself twoAlcohol diacrylate, initator is benzophenone;
(5) casting solution in step (4) is filtered with 300 object copper mesh;
(6) casting solution step (5) being filtered leaves standstill two days to remove bubble;
(7) by the degassed casting solution film of step (6) gained on Kynoar counterdie;
(8) the UV-crosslinked 40min of composite membrane step (7) being obtained;
(9) composite membrane step (8) being obtained is put into deionized water and is carried out exchange of solvent, obtains active layerThickness is the ethyl cellulose infiltrating and vaporizing membrane of 30-50 μ m.
2. the preparation method of ethyl cellulose permeable vaporized gasoline desulphurization membrane according to claim 1,It is characterized in that: the composite membrane that step (7) is obtained is placed in 1h at 60 DEG C of solvent vapo(u)r constant temperature and carries out moltenAgent annealing in process is carried out the UV-crosslinked of step (8) again.
3. the preparation method of ethyl cellulose permeable vaporized gasoline desulphurization membrane according to claim 2,It is characterized in that: the solvent adopting is thiophene, benzene, cyclohexene, cyclohexane or normal heptane.
4. the preparation method of ethyl cellulose permeable vaporized gasoline desulphurization membrane according to claim 3,It is characterized in that, ethyl cellulose infiltrating and vaporizing membrane is for gasoline desulfur.
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| CN103990389B (en) * | 2014-06-03 | 2016-05-25 | 天津工业大学 | A kind of Supermolecular film and manufacture method thereof |
| CN106334458A (en) * | 2016-10-20 | 2017-01-18 | 合肥创想能源环境科技有限公司 | Method for preparing crosslinking HEC pervaporation membrane for gasoline desulfurization |
| CN106422814B (en) * | 2016-10-28 | 2019-07-09 | 西北大学 | A kind of sodium carboxymethylcellulose infiltration evaporation desulfurizing film and preparation method thereof |
| CN106606934A (en) * | 2016-12-02 | 2017-05-03 | 中国石油大学(华东) | Polyurethane pervaporation recovered solvent membrane and preparation method thereof |
| CN109251765B (en) | 2018-10-31 | 2020-05-05 | 中国石油大学(华东) | Polyurethane/polyvinylidene fluoride composite membrane for extracting organic sulfide from naphtha and preparation method thereof |
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| US8617395B2 (en) * | 2010-09-30 | 2013-12-31 | The United States Of America, As Represented By The Secretary Of Agriculture | Thin film composite membranes and their method of preparation and use |
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