CN104437141A - Preparation method of solvent resistant nanofiltration membrane - Google Patents
Preparation method of solvent resistant nanofiltration membrane Download PDFInfo
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- CN104437141A CN104437141A CN201410652250.3A CN201410652250A CN104437141A CN 104437141 A CN104437141 A CN 104437141A CN 201410652250 A CN201410652250 A CN 201410652250A CN 104437141 A CN104437141 A CN 104437141A
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- fluorosioloxane rubber
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Abstract
The invention discloses a preparation method of a solvent resistant nanofiltration membrane. The preparation method comprises the steps of dissolving fluorosilicone oil, a cross-linking agent and a catalyst in a solvent, fully stirring to prepare a casting solution, filtering, defoaming, controlling the thickness, uniformly coating a base membrane by the casting solution, placing at room temperature until the solvent is volatized and solidified preliminarily, and further crosslinking at certain room temperature to obtain the fluorinated silicone rubber solvent resistant nanofiltration membrane. The prepared solvent resistant nanofiltration membrane is used for recycling hexane from soybean oil/hexane mixed oil, has excellent separation property, can overcome the disadvantage that the common silicone rubber has organic solvent intolerance, has excellent swelling resisting behavior, and can keep stable separating property after long-time operation.
Description
Technical field
The invention belongs to organic film separation technology field, particularly a kind of preparation method of solvent resistant NF membrane.
Background technology
Organic solvent soaking extraction is the prevailing technology in current vegetable oil process, extracting solvent mainly adopts hexane or No. six solvent naphthas based on hexane, extracting solvent is contacted in infuser with oil plant, obtain the miscella containing more vegetable oil, wherein content of vegetable oil is generally between 20%-30%.Existing technique usually adopts the method recycling design of evaporation and obtains vegetable oil, and energy consumption is huge.
Nanofiltration is a kind of is motive force with pressure, isolates the membrane separating process of solvent from solution.Adopt nanofiltration recycling design from miscella, owing to there is no evaporation process, can mass energy be saved.In vegetable oil production, substantially have a large amount of solvents to need to reclaim, so the market of embrane method recycling design is very large, potential energy-saving benefit is considerable.Up to the present, not yet the membrane material that separating property is good, stability is strong is found.And the separating property evaluating NF membrane mainly contains two indices, i.e. the flux of NF membrane and selective, stability evaluates the another one important indicator of NF membrane, and can steady in a long-termly run be that NF membrane realizes industrialized key in specific system.But most of NF membrane is not good to the separating property of miscella, flux is large but rejection is low, or rejection is high but flux is too low, or flux and rejection all low.Have also discovered the membrane material on a small quantity with better separating property at present, as dimethyl silicone polymer, but its in hexane seriously swelling, to the poor stability of miscella, run in miscella and namely start quick decline less than 100 hours separating properties, this makes it cannot extensive use in the industry.
Summary of the invention
The advantages such as solving the problems of the technologies described above, the invention provides a kind of preparation method of solvent resistant NF membrane, it is good that prepared solvent resistant NF membrane has separating property, and solvent tolerance is strong, and mechanical strength is high, and longtime running is stable.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for fluorosioloxane rubber solvent resistant NF membrane, is characterized in that, comprise the following steps:
(1) preparation of fluorosioloxane rubber casting solution: fluorosilicon oil is dissolved in organic solvent, be configured to the solution that concentration is 5% ~ 70%, stirring and dissolving, then in solution, crosslinking agent and catalyst is dripped, stir, obtain fluorosioloxane rubber casting solution after filtration, deaeration, wherein the consumption of crosslinking agent is 3% ~ 15% of fluorosilicon oil quality, and the consumption of catalyst is 2% ~ 5% of fluorosilicon oil quality;
(2) preparation of NF membrane: by fluorosioloxane rubber casting solution knifing on counterdie of preparation in step (1), room temperature is placed, and after solvent volatilization also primary solidification, keeps 80 DEG C ~ 160 DEG C heat treatments 12 ~ 48 hours in an oven, make it completely crosslinked, obtained fluorosioloxane rubber solvent resistant NF membrane.
Fluorosilicon oil described in step (1), the partial side-chain in its structure is γ-trifluoro propyl, and is end group with hydroxyl.
Wherein, the side chain number containing γ-trifluoro propyl in the structure of described fluorosilicon oil accounts for the 30%-100% of total side chain number.
Organic solvent described in step (1) be to fluorosilicon oil have in the toluene of good solubility, heptane, hexane, acetone, butanone, pentanone or acetyl butyryl any one or a few.
Crosslinking agent described in step (1) is the one of ethyl orthosilicate, octyl group trimethoxy silane, γ aminopropyltriethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane or containing hydrogen silicone oil.
Catalyst described in step (1) is dibutyl tin laurate or dibutyltin diacetate.
Counterdie described in step (2) is porous milipore filter organic solvent to better stability, and its membrane material is any one in Kynoar, polyimides or PEI.
Tool of the present invention has the following advantages: method provided by the present invention is simple, and cost is low, and prepared solvent resistant nano filter membrane separating property is good, solvent tolerance is strong, mechanical strength is high, and in longtime running, separating property keeps stable, has great industrial applications potentiality.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture on the fluorosioloxane rubber solvent resistant NF membrane surface prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscopic picture of the fluorosioloxane rubber solvent resistant NF membrane section prepared by the embodiment of the present invention 1.
Fig. 3 is the fluorosioloxane rubber solvent resistant NF membrane long term stability tests figure prepared by the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is further described, but protection scope of the present invention is not limited thereto.
Following examples are for the side chain of fluorosilicon oil for γ-trifluoro propyl and methyl, and molecular structural formula is as follows:
。
Embodiment 1
(1) prepare Kynoar (PVDF) counterdie: be placed in baking oven by PVDF raw material and dewater, be then made into for solvent the solution that PVDF mass concentration is 15% with triethyl phosphate (TEP), at 100 DEG C, stir 24 h; After filtration, vacuum defoamation, taking water as coagulation bath, adopt immersion precipitation phase inversion process knifing on non-woven fabrics, obtain pvdf membrane, finally fully wash away solvent by deionized water, dry, obtain PVDF ultrafiltration membrane, is also the counterdie of fluorosioloxane rubber solvent resistant NF membrane.
(2) fluorosioloxane rubber casting solution is prepared: mix accounting for the fluorosilicon oil of total side chain number 50%, phenyltrimethoxysila,e, dibutyltin diacetate and butanone containing γ-trifluoro propyl side chain number, stir, filter, fluorosioloxane rubber casting solution is obtained, wherein fluorosilicon oil: phenyltrimethoxysila,e: dibutyltin diacetate: the mass ratio of butanone is 7:0.7:0.21:3 after deaeration.
(3) fluorosioloxane rubber NF membrane is prepared, be coated in by the fluorosioloxane rubber casting solution that step (2) obtains on the obtained PVDF counterdie of step (1), room temperature places 24 hours, after solvent volatilization also primary solidification, 120 DEG C of heat treatment 30 hours in an oven, obtained fluorosioloxane rubber solvent resistant NF membrane.
As depicted in figs. 1 and 2, be respectively the surface of fluorosioloxane rubber solvent resistant NF membrane and the scanning electron microscopic picture of section, the surface of NF membrane is fine and close continuous uniform as seen from Figure 1, does not have defect
,fig. 3 is NF membrane permeation flux-time plot and rejection-time plot, i.e. long term stability tests figure, known by Fig. 3, keeps stable in separating property in the test process of 31 days.
Calculate permeation flux by formula (1), calculate rejection by formula (2); Formula (1) and formula (2) as follows:
。
In formula (1)
jrefer to permeation flux (k), refer to the amount of substance of component of mixture diffuse transmission film in unit interval unit are, be used for characterizing the speed of infiltration component through film;
mrefer to the quality (kg) of permeate;
afor effective film area (m
2);
tfor the operating time (h).
In formula (2)
rrefer to rejection, represent the separating effect of NF membrane to hexane and soybean oil, wherein
c ffor the concentration of oil in material liquid,
c pfor the concentration of oil in permeate; Rejection
rsize between 0 ~ 100%,
rlarger, illustrate that the soybean oil in permeate is fewer, separating effect is better.
The fluorosioloxane rubber solvent resistant NF membrane obtained to the present embodiment carries out the test of miscella separating property: by soybean oil content be 29% soybean oil/hexane miscella be 25 DEG C at feeding temperature, feed pressure is flow through NF membrane surface under 2.1 MPa, under the effect of the pressure, solvent and a small amount of soybean oil overcome osmotic pressure through NF membrane, obtain the penetrating fluid that oil content is lower, permeation flux is 1.1 kgm after testing
-2h
-1, be 95.5% to the rejection of soybean oil.
Embodiment 2
(1) prepare PEI (PEI) counterdie: be placed in baking oven by PEI raw material and dewater, with dimethylacetylamide (DMAC) for solvent, 1-METHYLPYRROLIDONE is additive, is made into the solution that PEI mass concentration is 15%, stirs 24 h; After filtration, vacuum defoamation, take water as coagulation bath, adopt immersion precipitation phase inversion process knifing on non-woven fabrics, obtain PEI film.Gained film deionized water fully being washed away solvent, dries, obtain PEI milipore filter, is also the counterdie of fluorosioloxane rubber solvent resistant NF membrane.
(2) fluorosioloxane rubber casting solution is prepared: mix accounting for the fluorosilicon oil of total side chain number 50%, octyl group trimethoxy silane, dibutyltin diacetate and pentanone containing γ-trifluoro propyl side chain number, stir, filter, fluorosioloxane rubber casting solution is obtained, wherein fluorosilicon oil: octyl group trimethoxy silane: dibutyltin diacetate: the mass ratio of pentanone is 10:1:0.3:120 after deaeration.
(3) fluorosioloxane rubber NF membrane is prepared: be coated in by the fluorosioloxane rubber casting solution that step (2) obtains on the obtained PEI counterdie of step (1), room temperature places 24 hours, until solvent volatilization and after primary solidification, 120 DEG C of heat treatment 48 hours in an oven, obtained fluorosioloxane rubber solvent resistant NF membrane.
The fluorosioloxane rubber solvent resistant NF membrane obtained by the present embodiment is used for the test of miscella separating property, and test result is as shown in table 1.
The separating property of table 1 fluorosioloxane rubber NF membrane under different temperatures, pressure
According to solubility-diffusion model, in nanofiltration process, the flux of solvent can be expressed as
, wherein
j i for the flux of hexane,
pfor infiltration coefficient,
for the difference of pressure reduction and osmotic pressure.As seen from the above table, when feed pressure is constant, when soybean oil concentration raises, osmotic pressure increases, and motive force reduces, and therefore permeation flux declines.At various concentrations, in table 1, penetrating fluid oil content is all less than 3%, lower than the recovery standard of leaching vegetable oil hexane used, can direct reuse as leaching liquid.
Embodiment 3
(1) Kynoar (PVDF) counterdie is prepared: method is with step (1) in embodiment 1.
(2) fluorosioloxane rubber casting solution is prepared: mix accounting for the fluorosilicon oil of total side chain number 50%, hydrogen silicone oil, dibutyl tin laurate and butanone containing γ-trifluoro propyl side chain number, stir, filter, fluorosioloxane rubber casting solution is obtained, wherein fluorosilicon oil: hydrogen silicone oil: dibutyl tin laurate: the mass ratio of butanone is 10:0.3:0.3:50 after deaeration.
(3) fluorosioloxane rubber NF membrane is prepared: be coated in by the fluorosioloxane rubber casting solution that step (2) obtains on the obtained PVDF counterdie of step (1), room temperature places 24 hours, until solvent volatilization and after primary solidification, 120 DEG C of heat treatment 36 hours in an oven, obtained fluorosioloxane rubber solvent resistant NF membrane.
The fluorosioloxane rubber solvent resistant NF membrane obtained to the present embodiment is used for the test of miscella separating property: by soybean oil content be 28% soybean oil/hexane miscella be 25 DEG C at feeding temperature, feed pressure is flow through NF membrane surface under 2.1 MPa, and permeation flux is 11.5 kgm after testing
-2h
-1, be 95.1% to the rejection of soybean oil.
Embodiment 4
(1) PEI (PEI) counterdie is prepared: method is with step (1) in embodiment 2.
(2) fluorosioloxane rubber casting solution is prepared, the mixing of the fluorosilicon oil of total side chain number 30%, ethyl orthosilicate, dibutyl tin laurate and toluene will be accounted for containing γ-trifluoro propyl side chain number, stir, filter, fluorosioloxane rubber casting solution is obtained, wherein fluorosilicon oil: ethyl orthosilicate: dibutyltin diacetate: the mass ratio of toluene is 10:1:0.3:100 after deaeration.
(3) fluorosioloxane rubber NF membrane is prepared, be coated in by the fluorosioloxane rubber casting solution that step (2) obtains on the obtained PEI counterdie of step (1), room temperature places 24 hours, after solvent volatilization also primary solidification, 80 DEG C of heat treatment 12 hours in an oven, obtained fluorosioloxane rubber solvent resistant NF membrane.
The fluorosioloxane rubber solvent resistant NF membrane obtained by the present embodiment is used for the test of miscella separating property: when soybean oil content in miscella be 23%, feeding temperature is 25 DEG C, feed pressure 2.4 MPa time, permeation flux is 15.8 kgm after testing
-2h
-1, be 96.5% to the rejection of soybean oil.
Embodiment 5
(1) Kynoar (PVDF) counterdie is prepared: method is with step (1) in embodiment 1.
(2) fluorosioloxane rubber casting solution is prepared, the mixing of the fluorosilicon oil of total side chain number 50%, phenyltrimethoxysila,e, dibutyl tin laurate and acetyl butyryl will be accounted for containing γ-trifluoro propyl side chain number, stir, filter, fluorosioloxane rubber casting solution is obtained, wherein fluorosilicon oil: phenyltrimethoxysila,e: dibutyltin diacetate: the mass ratio of acetyl butyryl is 10:1:0.3:60 after deaeration.
(3) fluorosioloxane rubber NF membrane preparation, be coated in by the fluorosioloxane rubber casting solution that step (2) obtains on the obtained PVDF counterdie of step (1), room temperature places 24 hours, after solvent volatilization also primary solidification, 150 DEG C of heat treatment 48 hours in an oven, obtained fluorosioloxane rubber solvent resistant NF membrane.
The fluorosioloxane rubber solvent resistant NF membrane obtained by the present embodiment is used for the test of miscella separating property: when soybean oil content in miscella be 28%, feeding temperature is 25 DEG C, feed pressure is 2.4 MPa time, permeation flux is 3.5 kgm
-2h
-1, be 98.6% to the rejection of soybean oil.
Embodiment 6
(1) Kynoar (PVDF) counterdie is prepared: method is with step (1) in embodiment 1.
(2) fluorosioloxane rubber casting solution is prepared, the mixing of the fluorosilicon oil of total side chain number 100%, phenyltrimethoxysila,e, dibutyl tin laurate and butanone will be accounted for containing γ-trifluoro propyl side chain number, stir, filter, fluorosioloxane rubber casting solution is obtained, wherein fluorosilicon oil: phenyltrimethoxysila,e: dibutyltin diacetate: the mass ratio of butanone is 10:1.2:0.4:30 after deaeration.
(3) fluorosioloxane rubber NF membrane is prepared, be coated in by the fluorosioloxane rubber casting solution that step (2) obtains on the obtained PVDF counterdie of step (1), room temperature places 24 hours, after solvent volatilization also primary solidification, 130 DEG C of heat treatment 48 hours in an oven, obtained fluorosioloxane rubber solvent resistant NF membrane.
The fluorosioloxane rubber solvent resistant NF membrane obtained by the present embodiment is used for the test of miscella separating property: when soybean oil content in miscella be 28%, feeding temperature is 25 DEG C, feed pressure is 2.4 MPa time, permeation flux is 1.5 kgm after testing
-2h
-1, be 95.3% to the rejection of soybean oil.
Embodiment 7
(1) PEI (PEI) counterdie is prepared: method is with step (1) in embodiment 2.
(2) fluorosioloxane rubber casting solution is prepared, the mixing of the fluorosilicon oil of total side chain number 30%, phenyl triethoxysilane, dibutyl tin laurate and toluene will be accounted for containing γ-trifluoro propyl side chain number, stir, filter, fluorosioloxane rubber casting solution is obtained, wherein fluorosilicon oil: phenyltrimethoxysila,e: dibutyltin diacetate: the mass ratio of toluene is 5:0.75:0.1:100 after deaeration.
(3) fluorosioloxane rubber NF membrane preparation, be coated in by the fluorosioloxane rubber casting solution that step (2) obtains on the obtained PEI counterdie of step (1), room temperature places 24 hours, after solvent volatilization also primary solidification, 160 DEG C of heat treatment 12 hours in an oven, obtained fluorosioloxane rubber solvent resistant NF membrane.
The fluorosioloxane rubber solvent resistant NF membrane obtained by the present embodiment is used for the test of miscella separating property: when soybean oil content in miscella be 26%, feeding temperature is 25 DEG C, feed pressure is 2.4 MPa time, permeation flux is 13.2 kgm
-2h
-1, be 95.6% to the rejection of soybean oil.
Embodiment 8
(1) PEI (PEI) counterdie is prepared: method is with step (1) in embodiment 2.
(2) fluorosioloxane rubber casting solution is prepared, the mixing of the fluorosilicon oil of total side chain number 100%, phenyltrimethoxysila,e, dibutyl tin laurate and butanone will be accounted for containing γ-trifluoro propyl side chain number, stir, filter, fluorosioloxane rubber casting solution is obtained, wherein fluorosilicon oil: phenyltrimethoxysila,e: dibutyltin diacetate: the mass ratio of butanone is 10:1.5:0.5:30 after deaeration.
(3) fluorosioloxane rubber NF membrane is prepared, be coated in by the fluorosioloxane rubber casting solution that step (2) obtains on the obtained PEI counterdie of step (1), room temperature places 24 hours, after solvent volatilization also primary solidification, 150 DEG C of heat treatment 48 hours in an oven, obtained fluorosioloxane rubber solvent resistant NF membrane.
The fluorosioloxane rubber solvent resistant NF membrane obtained by the present embodiment is used for the test of miscella separating property: when soybean oil content in miscella be 22%, feeding temperature is 25 DEG C, feed pressure is 2.4 MPa time, permeation flux is 1.4 kgm after testing
-2h
-1, be 95.8% to the rejection of soybean oil.
Can be drawn by above-described embodiment, the solvent resistant NF membrane prepared by the present invention, permeation flux reaches as high as 15.8 kgm
-2h
-1rejection is up to 98.6%, penetrating fluid can leach in vegetable oil by direct reuse, and the solvent resistant NF membrane prepared by the present invention breaches the shortcoming of usual silicone rubber not organic solvent-resistant, there is excellent swelling resistance performance, have good stability, in longtime running, separating property keeps stable, has great industrial applications potentiality.
Finally should be noted that: the catalyst described in step (1) also can be other organic tin catalyst.
Above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit, and to not departing from any amendment of spirit and scope of the invention or equivalent replacement, it all should be encompassed in the middle of right of the present invention.
Claims (7)
1. a preparation method for fluorosioloxane rubber solvent resistant NF membrane, is characterized in that, comprises the following steps:
(1) preparation of fluorosioloxane rubber casting solution: fluorosilicon oil is dissolved in organic solvent, be configured to the solution that mass concentration is 5% ~ 70%, in solution, crosslinking agent and catalyst is dripped after stirring and dissolving, the consumption of crosslinking agent is 3% ~ 15% of fluorosilicon oil quality, the consumption of catalyst is 2% ~ 5% of fluorosilicon oil quality, then stir, after filtration, deaeration, obtain fluorosioloxane rubber casting solution;
(2) preparation of NF membrane: by fluorosioloxane rubber casting solution knifing on counterdie of preparation in step (1), room temperature is placed, and after solvent volatilization also primary solidification, keeps 80 DEG C ~ 160 DEG C heat treatments 12 ~ 48 hours in an oven, make it completely crosslinked, obtained fluorosioloxane rubber solvent resistant NF membrane.
2. the preparation method of a kind of fluorosioloxane rubber solvent resistant NF membrane according to claim 1, it is characterized in that, the fluorosilicon oil described in step (1), the partial side-chain in its structure is γ-trifluoro propyl, and is end group with hydroxyl.
3. the preparation method of a kind of fluorosioloxane rubber solvent resistant NF membrane according to claim 2, is characterized in that, the side chain number containing γ-trifluoro propyl in the structure of described fluorosilicon oil accounts for the 30%-100% of total side chain number.
4. the preparation method of a kind of fluorosioloxane rubber solvent resistant NF membrane according to claim 1, it is characterized in that, the organic solvent described in step (1) be to fluorosilicon oil have in the toluene of good solubility, heptane, hexane, acetone, butanone, pentanone or acetyl butyryl any one or a few.
5. the preparation method of a kind of fluorosioloxane rubber solvent resistant NF membrane according to claim 1, it is characterized in that, the crosslinking agent described in step (1) is the one of ethyl orthosilicate, octyl group trimethoxy silane, γ aminopropyltriethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane or containing hydrogen silicone oil.
6. the preparation method of a kind of fluorosioloxane rubber solvent resistant NF membrane according to claim 1, it is characterized in that, the catalyst described in step (1) is dibutyl tin laurate or dibutyltin diacetate.
7. the preparation method of a kind of fluorosioloxane rubber solvent resistant NF membrane according to claim 1, it is characterized in that, described in step (2), counterdie is porous milipore filter, and its membrane material is any one in Kynoar, polyimides or PEI.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179000A (en) * | 2016-08-18 | 2016-12-07 | 贵阳时代沃顿科技有限公司 | A kind of preparation method of solvent resistant NF membrane |
| CN106582314A (en) * | 2017-02-26 | 2017-04-26 | 浙江理工大学 | Preparation method of small-pore-size hydrophobic composite membrane used for membrane distillation |
| CN112495194A (en) * | 2020-10-09 | 2021-03-16 | 北京迈安瑞科技有限公司 | Preparation method of silicone rubber gas separation coating |
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| CN1718665A (en) * | 2005-06-21 | 2006-01-11 | 广州市白云化工实业有限公司 | Organic silicon fluoro water proofing agent and its preparation method |
| CN101077799A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院化学研究所 | Infiltration vaporization blending composite film for removing phenols from waste water |
| CN103131193A (en) * | 2013-02-18 | 2013-06-05 | 湖北派克密封件有限公司 | Fluorosilicone rubber sealing material and preparation method thereof for proton exchanging membrane battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1718665A (en) * | 2005-06-21 | 2006-01-11 | 广州市白云化工实业有限公司 | Organic silicon fluoro water proofing agent and its preparation method |
| CN101077799A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院化学研究所 | Infiltration vaporization blending composite film for removing phenols from waste water |
| CN103131193A (en) * | 2013-02-18 | 2013-06-05 | 湖北派克密封件有限公司 | Fluorosilicone rubber sealing material and preparation method thereof for proton exchanging membrane battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106179000A (en) * | 2016-08-18 | 2016-12-07 | 贵阳时代沃顿科技有限公司 | A kind of preparation method of solvent resistant NF membrane |
| CN106582314A (en) * | 2017-02-26 | 2017-04-26 | 浙江理工大学 | Preparation method of small-pore-size hydrophobic composite membrane used for membrane distillation |
| CN112495194A (en) * | 2020-10-09 | 2021-03-16 | 北京迈安瑞科技有限公司 | Preparation method of silicone rubber gas separation coating |
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