CN104383819B - The preparation method that a kind of micro porous molecular sieve fills solvent resistant composite membrane - Google Patents
The preparation method that a kind of micro porous molecular sieve fills solvent resistant composite membrane Download PDFInfo
- Publication number
- CN104383819B CN104383819B CN201410652268.3A CN201410652268A CN104383819B CN 104383819 B CN104383819 B CN 104383819B CN 201410652268 A CN201410652268 A CN 201410652268A CN 104383819 B CN104383819 B CN 104383819B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- composite membrane
- micro porous
- preparation
- resistant composite
- 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 invention discloses the preparation method that a kind of micro porous molecular sieve fills solvent resistant composite membrane, fluorosilicon oil, micro porous molecular sieve, cross-linking agent, catalyst and solvent are configured to casting solution, with solvent resistant ultrafilter membrane for counterdie, casting solution are coated on counterdie uniformly; After solvent volatilization solidifies, further heating makes its deep-crosslinked, obtains micro porous molecular sieve and fills solvent resistant composite membrane. Composite membrane prepared by the present invention, molecular sieve is uniformly dispersed in stratum disjunctum, concurrently separate layer to be tightly combined with supporting layer, there is good swelling resistance in organic solvent, during for reclaiming low molecular weight solvent from miscella, separating effect is excellent, and stability is strong, and in long-play, separating property remains stable for.
Description
Technical field
The present invention relates to solvent resistant composite membrane technology field, particularly to the preparation method that a kind of micro porous molecular sieve reclaimed suitable in low-molecular-weight organic solvent fills solvent resistant composite membrane.
Background technology
At production fields such as chemical industry, having substantial amounts of rectification, distillation etc. to relate to the separation process of vaporization, owing to the latent heat of vaporization is general higher, these process energy consumptions are significantly high. Nanofiltration is a kind of with pressure for motive force, isolates the membrane separating process of solvent from solution. Adopt nanofiltration recycling design from miscella, owing to there is no evaporation process, it is possible to save mass energy.
Current industrial oil-producing technique mainly has milling process and solvent extraction method. Solvent extraction method liquefaction includes direct leaching, pre-squeezing-three kinds of methods such as leaching and secondary leaching. Direct leaching is mainly used in the low oil such as Semen sojae atricolor, Semen Gossypii, Testa oryzae and divides oil plant; Prepressing extraction or secondary leach and are mainly used in the high-oil-content materials such as castor bean, Semen arachidis hypogaeae, Semen Allii Tuberosi, sunflower seed, Semen Lini.
Compared with milling process, solvent extraction method has plurality of advantages, such as oil yield high (94～99%), dry meal residual oil rate low (0.5～1.5%), can obtain high-quality crude oil and the dregs of rice of low degeneration, it may be achieved serialization and automated production, productivity ratio is high, and power consumption is low, and labor intensity is low. Due to this series of advantage, leaching refining method has become the prevailing technology of current oils preparation industry, and the application percentage in developed country is generally more than 90%.
Extracting solvent mainly adopts hexane or No. six solvent naphthas based on hexane, and vegetable oil/soy solution that leaching obtains is commonly referred to miscella. In miscella, content of vegetable oil is typically between 20%-30%. For reclaiming solution, also obtaining crude oil, existing technique generally adopts evaporation technology, and energy consumption is huge simultaneously.
The eighties in last century, the hexane that American Oil processing industry need to be reclaimed every year about 7,000,000 tons, adopt evaporation technology. According to estimates, evaporation is replaced to reclaim according to embrane method, every year can saving heat energy 2.1 × 1021J. Chinese 2012 soybean oil consumptions 12,810,000 tons, whole world soybean oil consumption then reaches 41,000,000 tons, estimates with this, it is necessary to the hexane of recovery is more than 100,000,000 tons. Reclaiming owing to there being substantial amounts of solvent to need in other vegetable oil production of Semen Allii Tuberosi wet goods equally, the market of embrane method recycling design is huge, and potential energy-saving benefit is considerable.
In view of this, from the eighties in last century, namely researcher is studied, but up to the present, not yet finds desirable membrane material. Most membrane material is not good to the separating property of miscella, and flux is big but the rejection of soybean oil is low, or soybean oil rejection is high but flux is too low, or flux and soybean oil rejection all low. Have also discovered the membrane material on a small quantity with better separating property, such as polydimethylsiloxane, but it in hexane swelling seriously, the poor stability to miscella, running in miscella and namely start rapid decrease less than 100 hours separating properties, this makes it cannot commercial Application.
Accordingly, it is desirable to provide a kind of new technical scheme solves the problems referred to above.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method that a kind of micro porous molecular sieve fills solvent resistant composite membrane. The advantages such as it is good that prepared solvent resistant composite membrane has separating property, swelling resistance, and mechanical strength is high, and longtime running is stable.
For solving above-mentioned technical problem, the preparation method that a kind of micro porous molecular sieve of the present invention fills solvent resistant composite membrane, comprise the following steps:
Step 1: molecular sieve pretreatment
Micro porous molecular sieve granular powder is broken to particle diameter less than 2 microns, add organic solvent, stirring is scattered and is configured to suspension ultrasonic disperse 1-2 hour, silane coupler is dripped in suspension, silane coupler quality is the 10% ~ 50% of molecular sieve quality, and room temperature, to 80 DEG C, stirs 1～12 hour, filter, wash post-drying, obtain the molecular sieve that silane coupler is modified;
Step 2: the preparation of casting solution
Fluorosilicon oil is dissolved in organic solvent, it is configured to the solution that mass concentration is 10% ~ 70%, stirring and dissolving, add the molecular sieve after modifying, it is sufficiently stirred for rear ultrasonic disperse 1～5 hour, with backward solution is sequentially added into cross-linking agent and catalyst, the consumption of molecular sieve, cross-linking agent and catalyst respectively the 5% ~ 30% of fluorosilicon oil quality, 3% ~ 15%, 2% ~ 5%, stir, obtain casting solution;
Step 3: the preparation of composite membrane
With solvent-proof ultrafilter membrane for counterdie, casting solution in step 2 is coated uniformly on counterdie, room temperature is placed a period of time to 60 DEG C and is treated solvent volatilization primary solidification, keep 80 DEG C ~ 160 DEG C in an oven subsequently, heat treatment makes it full cross-linked in 12 ~ 48 hours, prepares molecular sieve filled solvent resistant composite membrane.
In above-mentioned preparation method, the micropore size of the micro porous molecular sieve used by step 1 is between 0.5～1.0nm, it is possible to select the molecular sieve of ZSM-5, Silicalite or Modernite.
In above-mentioned preparation method, the silane coupler used by step 1 is trim,ethylchlorosilane, chlorotriethyl silane, butyl Ethoxysilane, octyl group trimethoxy silane or hexadecyl trichlorosilane; Its hydrolyzable groups is chloro, methoxyl group, ethyoxyl or acetyl chloro, and organo-functional group is methyl, ethyl, butyl, hexyl, octyl group, dodecyl or cetyl.
In above-mentioned preparation method, the fluorosilicon oil used by step 2, partial side-chain is γ-trifluoro propyl, to contain part of hydroxyl on hydroxy-end capped or main chain.
In above-mentioned preparation method, fluorosilicon oil used in step 2, the chain hop count wherein containing γ-trifluoro propyl side chain accounts for the 30%-100% of total chain hop count.
In above-mentioned preparation method, cross-linking agent used in step 2 is any one in tetraethyl orthosilicate, octyl group trimethoxy silane, γ aminopropyltriethoxy silane, phenyltrimethoxysila,e, phenyl three TMOS, containing hydrogen silicone oil.
In above-mentioned preparation method, catalyst used in step 2 is organic tin catalyst, and described organic tin catalyst is dibutyl tin laurate or dibutyl dibutyltin diacetate.
In above-mentioned preparation method, organic solvent used in step 1 is toluene, dimethylbenzene or heptane; Organic solvent used in step 2 is acetone, butanone, pentanone, acetyl butyryl, toluene, dimethylbenzene or heptane.
In above-mentioned preparation method, ultrafilter membrane used in step 3 is any one in Kynoar, polyimides, Polyetherimide.
Composite membrane prepared by the present invention, molecular sieve is uniformly dispersed in stratum disjunctum, concurrently separate layer to be tightly combined with supporting layer, there is good swelling resistance in organic solvent, during for reclaiming low molecular weight solvent from miscella, separating effect is excellent, and stability is strong, and in long-play, separating property remains stable for.
Accompanying drawing explanation
The duct that Fig. 1 is Middle molecule of the present invention sieve can make hexane pass through the schematic diagram hindering soybean oil to pass through.
Fig. 2 is the test device of composite membrane separating property in the present invention.
Wherein: 1, pulse damper, 2, thermometer, 3, film room, 4, Pressure gauge, 5, counterbalance valve, 6, material liquid tank, 7, high-pressure metering pump, 8, radiator valve.
Detailed description of the invention
In order to deepen the understanding of the present invention, below in conjunction with embodiment and accompanying drawing, the invention will be further described, and this embodiment is only used for explaining the present invention, is not intended that the restriction to protection scope of the present invention.
The specific embodiment of the preparation method that a kind of micro porous molecular sieve of the present invention fills solvent resistant composite membrane is as follows:
Embodiment 1
The ZSM-5 molecular sieve that silica alumina ratio is 300 being crushed to particle diameter less than 2 microns, add toluene and be configured to the suspension ultrasonic disperse 1 hour that mass concentration is 20%, be subsequently added the octyltrichlorosilane of ZSM-5 mass 10%, 80 DEG C are stirred 12 hours. Filter, wash post-drying, obtain the ZSM-5 that octyltrichlorosilane is modified. Take 10 grams of γ-trifluoro propyl side chain chain hop count to account for the fluorosilicon oil of total chain hop count 50% and be dissolved in 20 grams of butanone, add the ZSM-5 after 2 grams of modifications, ultrasonic disperse 1 hour after stirring, sequentially add 1 gram of phenyltrimethoxysila,e and 0.3 gram of dibutyltin diacetate, casting solution is obtained after stirring, with PVDF ultrafiltration membrane for counterdie, knifing on counterdie. After room temperature is placed 24 hours, 80 DEG C are heated 48 hours in an oven so that it is full cross-linked, prepare ZSM-5 molecular sieve and fill solvent resistant composite membrane.
Prepared composite membrane is used for the test of miscella separating property, when in miscella soybean oil content be 26%, feeding temperature be 25 DEG C, feed pressure 2.4MPa time, permeation flux 2.5kg m-2·h-1, rejection 96.2% to soybean oil. During for stability test, the separating property during test remains stable for, as shown in table 1.
Table 1 micro porous molecular sieve fills the stability test of solvent resistant composite membrane
Embodiment 2
The ZSM-5 molecular sieve that silica alumina ratio is 300 is crushed to particle diameter less than 2 microns, adds toluene and be configured to the suspension ultrasonic disperse 1 hour that mass concentration is 20%, be subsequently added the octyl group trimethoxy silane of ZSM-5 mass 50%, be stirred at room temperature 1 hour. Filter, wash post-drying, obtain the ZSM-5 that octyl group trimethoxy silane is modified. Take 10 grams of γ-trifluoro propyl side chain chain hop count to account for the fluorosilicon oil of total chain hop count 30% and be dissolved in 90 grams of toluene, add the ZSM-5 after 3 grams of modifications, ultrasonic disperse 2 hours after stirring, sequentially add 1 gram of phenyltrimethoxysila,e and 0.2 gram of dibutyl tin laurate, casting solution is obtained after stirring, with PVDF ultrafiltration membrane for counterdie, knifing on counterdie. After room temperature is placed 24 hours, 120 DEG C are heated 12 hours in an oven so that it is full cross-linked, prepare ZSM-5 molecular sieve and fill solvent resistant composite membrane.
Prepared composite membrane is used for the test of miscella separating property, when in miscella soybean oil content be 25%, feeding temperature be 25 DEG C, feed pressure 2.4MPa time, permeation flux 8.2kg m-2·h-1, rejection 96.2% to soybean oil.
Embodiment 3
Silicate-1 molecular sieve being crushed to particle diameter less than 2 microns, add the suspension ultrasonic disperse 2 hours that toluene configuration quality concentration is 15%, be subsequently added the dodecyltrichlorosilane of silicate mass 20%, 50 DEG C are stirred 12 hours. Filter, wash post-drying, obtain the silicate-1 that dodecyltrichlorosilane is modified. Take the chain hop count of 14 grams of γ-trifluoro propyl side chain to account for the fluorosilicon oil of total chain hop count 50% and be dissolved in 6 grams of butanone, add the silicate-1 after 0.7 gram of modification, ultrasonic disperse 5 hours after stirring, sequentially add 1.5 grams of octyl group trimethoxy silanes and 0.4 gram of dibutyltin diacetate, after stirring, obtain casting solution. With PVDF ultrafiltration membrane for counterdie, knifing on counterdie. After room temperature is placed 24 hours, 120 DEG C are heated 24 hours in an oven so that it is full cross-linked, prepare the molecular sieve filled solvent resistant composite membrane of silicate-1.
Prepared composite membrane is used for the test of miscella separating property, when in miscella soybean oil content be 25%, feeding temperature be 25 DEG C, feed pressure 2.4MPa time, permeation flux 3.5kg m-2·h-1, rejection 96.6% to soybean oil.
Embodiment 4
Silicate-1 molecular sieve being crushed to particle diameter less than 2 microns, add the suspension ultrasonic disperse 2 hours that toluene configuration quality concentration is 15%, be subsequently added the hexadecyl trichlorosilane of silicate mass 20%, 50 DEG C are stirred 8 hours. Filter, wash post-drying, obtain the silicate-1 that hexadecyl trichlorosilane is modified. Take the chain hop count of 10 grams of γ-trifluoro propyl side chain to account for the fluorosilicon oil of total chain hop count 50% and be dissolved in 30 grams of butanone, add the silicate-1 after 1.5 grams of modifications, ultrasonic disperse 5 hours after stirring, sequentially add 1 gram of octyl group trimethoxy silane and 0.3 gram of dibutyltin diacetate, after stirring, obtain casting solution. With PVDF ultrafiltration membrane for counterdie, knifing on counterdie. After room temperature is placed 24 hours, 120 DEG C are heated 36 hours in an oven so that it is full cross-linked, prepare the molecular sieve filled solvent resistant composite membrane of silicate-1.
Prepared composite membrane is used for the test of miscella separating property, when in miscella soybean oil content be 28%, feeding temperature be 25 DEG C, feed pressure 2.4MPa time, permeation flux 7.6kg m-2·h-1, rejection 97.1% to soybean oil.
Embodiment 5
Silicate-1 molecular sieve is crushed to particle diameter less than 2 microns, adds the suspension ultrasonic disperse 1 hour that toluene configuration quality concentration is 15%, be subsequently added the dodecyltrichlorosilane of silicate mass 20%, 10% pyridine, 50 DEG C are stirred 12 hours. Filter, wash post-drying, obtain the silicate-1 that dodecyltrichlorosilane is modified. Take the chain hop count of 10 grams of γ-trifluoro propyl side chain to account for the fluorosilicon oil of total chain hop count 100% and be dissolved in 20 grams of pentanones, add the silicate-1 after 2.0 grams of modifications, ultrasonic disperse 4 hours after stirring, sequentially add 1.5 grams of tetraethyl orthosilicates and 0.5 gram of dibutyltin diacetate, casting solution is obtained after stirring, with PEI ultrafilter membrane for counterdie, knifing on counterdie. After room temperature is placed 24 hours, 160 DEG C are heated 12 hours in an oven so that it is full cross-linked, prepare the molecular sieve filled solvent resistant composite membrane of silicate-1.
Prepared composite membrane is used for the test of miscella separating property, when in miscella soybean oil content be 16%, feeding temperature be 25 DEG C, feed pressure 2.5MPa time, permeation flux 3.8kg m-2·h-1, rejection 97.2% to soybean oil.
Embodiment 6
Modernite molecular sieve is crushed to particle diameter less than 2 microns, adds the suspension ultrasonic disperse 1 hour that toluene configuration quality concentration is 20%, be subsequently added the octyl group trimethoxy silane of modernite mass 20%, be stirred at room temperature 8 hours. Filter, wash post-drying, obtain the modernite that octyl group trimethoxy silane is modified. Take the chain hop count of 10 grams of γ-trifluoro propyl side chain to account for the fluorosilicon oil of total chain hop count 50% and be dissolved in 20 grams of butanone, add the modernite after 3.0 grams of modifications, ultrasonic disperse 4 hours after stirring, sequentially add 0.3 gram of containing hydrogen silicone oil and 0.3 gram of dibutyltin diacetate, casting solution is obtained after stirring, with PVDF ultrafiltration membrane for counterdie, knifing on counterdie. After room temperature is placed 24 hours, 120 DEG C are heated 48 hours in an oven so that it is full cross-linked, prepare the molecular sieve filled solvent resistant composite membrane of modernite.
Prepared composite membrane is used for the test of miscella separating property, when in miscella soybean oil content be 26%, feeding temperature be 25 DEG C, feed pressure 2.5MPa time, permeation flux 4.8kg m-2·h-1, rejection 97.1% to soybean oil.
Comparative example:
Take the chain hop count of 10 grams of γ-trifluoro propyl side chain to account for the fluorosilicon oil of total chain hop count 50% and be dissolved in 20 grams of butanone, add the modernite molecular sieve of 3.0 grams of unmodifieds, ultrasonic disperse 4 hours after stirring, sequentially add 0.5 gram of containing hydrogen silicone oil and 0.3 gram of dibutyltin diacetate, casting solution is obtained after stirring, with PVDF ultrafiltration membrane for counterdie, knifing on counterdie. After room temperature is placed 24 hours, keep 120 DEG C in an oven and dry 48 hours so that it is be full cross-linked, prepare the molecular sieve filled solvent resistant composite membrane of unmodified modernite.
In above-described embodiment, prepared fluorosilicon oil solvent resistant NF membrane is used for the test of miscella separating property, when in miscella soybean oil content be 25%, feeding temperature be 25 DEG C, feed pressure 2.5MPa time, permeation flux 3.4kg m-2·h-1, rejection 96.0% to soybean oil. The modernite molecular sieve of unmodified poor dispersion in fluorosilicon oil stratum disjunctum, and hexane has repelling effect by the hydroxyl of molecular sieve surface, thus flux and rejection all decrease.
In the present invention, fluorosilicon oil replaces original side chain with γ-trifluoro propyl part, due to the repulsion to hexane and soybean oil of the γ-trifluoro propyl, can provide bigger shielding action for the main chain of PDMS, thus strengthening the stability of fluorosilicon oil greatly. It is called fluorosilicon oil, the molecular structural formula such as following formula when it is with hydroxy-end capped, side chain for γ-trifluoro propyl and methyl after the part or all of substituted for silicon rubber side-chain radical of γ-trifluoro propyl:;
Molecular structural formula such as following formula during with organic group end-blocking, side chain for γ-trifluoro propyl, methyl and hydroxyl:。
In molecular sieve pretreatment, molecular sieve is to have uniform micropore, the class material that its aperture is suitable with general molecular size. Conventional molecular sieve is silicate or the aluminosilicate of crystalline state, it is be connected by oxo bridge key by silicon-oxy tetrahedron or aluminum-oxygen tetrahedron and form duct and the cavity system of molecular dimension size (being generally 0.3 ~ 2nm), there is because binding molecule size is different with shape the ability sieving the fluid molecule varied in size.
In the preparation of casting solution, by molecular sieve filled in fluorosilicon oil, there are two effects:
1, promote the crosslinking of fluorosilicon oil, and increase the effect between fluorosilicon oil and molecular sieve, thus being greatly increased the degree of cross linking of composite membrane, toughness and stability;
If 2 as it is shown in figure 1, the duct of molecular sieve can make hexane pass through and hinder soybean oil to pass through, then can promoting the infiltration of hexane, and soybean oil lengthens due to mass transfer path, flux reduces.
Molecular sieve surface generally has hydrophilic radical, can not disperse preferably in casting solution, in serious place of reuniting, easily causes the local defect of composite membrane. For this, before use molecular sieve is carried out a degree of hydrophobically modified, it is possible to improve its dispersibility in casting solution.
Referring to Fig. 2, the test device of composite membrane separating property, to absorb hexane from soybean oil/hexane miscella in the way of nanofiltration.
Fig. 2 is the test device of composite membrane separating property, the input of film room 3, output pipe are respectively mounted thermometer 2 and Pressure gauge 4, installation counterbalance valve 5 on the pipeline of material liquid tank 6 is led in film room 3, bottom material liquid tank 6, output channel connects high-pressure metering pump 7, installing pulse damper 1 on high-pressure metering pump 7, radiator valve 8 regulates stationary temperature scope.
Uniform temperature, certain density miscella are flowed through composite film surface under pressure, and under the effect of the pressure, solvent and a small amount of soybean oil overcome osmotic pressure permeation composite membrane, obtain the penetrating fluid that oil content is relatively low, and concentrated solution feed back flow container continues cycling through.
Composite membrane is used for nanofiltration, and its separating property mainly has two indices, i.e. flux and selectivity.
1) composite membrane permeation flux is for characterizing the infiltration component speed through film, refers to that in unit interval unit are, component of mixture diffusion is through the amount of film, and its definition is:
Wherein, J refer to permeation flux (); M refers to the quality (kg) of permeate; A is effective film area (m2); T is the operating time (h).
2) rejection represents the NF membrane separating effect to hexane and soybean oil, and its definition is:
Wherein, cfFor the concentration of oil, c in material liquidpFor the concentration of oil in permeate. Rejection R is between 0～100%, and R is more big, illustrates that the soybean oil in permeate is more few, and separating effect is more good.
Can stability be the another one important indicator of evaluating combined film, steady in a long-term run, and this is that can composite membrane realize industrialized key in certain system.
Solvent resistant NF membrane prepared by the present invention, permeation flux reaches 5.3kg m-2·h-1, rejection is up to 98.5%, and penetrating fluid can leach in vegetable oil by direct reuse. What is more important, the solvent resistant NF membrane prepared by the present invention has good stability, and in longtime running, separating property remains stable for, and has great industrial applications potentiality.
Claims (9)
1. the preparation method that a micro porous molecular sieve fills solvent resistant composite membrane, it is characterised in that comprise the following steps:
Step 1: molecular sieve pretreatment
Micro porous molecular sieve granular powder is broken to particle diameter less than 2 microns, add organic solvent, stirring is scattered and is configured to suspension ultrasonic disperse 1-2 hour, silane coupler is dripped in suspension, silane coupler quality is the 10% ~ 50% of molecular sieve quality, and room temperature, to 80 DEG C, stirs 1～12 hour, filter, wash post-drying, obtain the molecular sieve that silane coupler is modified;
Step 2: the preparation of casting solution
Fluorosilicon oil is dissolved in organic solvent, it is configured to the solution that mass concentration is 10% ~ 70%, stirring and dissolving, add the molecular sieve after modifying, it is sufficiently stirred for rear ultrasonic disperse 1～5 hour, with backward solution is sequentially added into cross-linking agent and catalyst, the consumption of molecular sieve, cross-linking agent and catalyst respectively the 5% ~ 30% of fluorosilicon oil quality, 3% ~ 15%, 2% ~ 5%, stir, obtain casting solution;
Step 3: the preparation of composite membrane
With solvent-proof ultrafilter membrane for counterdie, casting solution in step 2 is coated uniformly on counterdie, room temperature is placed a period of time to 60 DEG C and is treated solvent volatilization primary solidification, keep 80 DEG C ~ 160 DEG C in an oven subsequently, heat treatment makes it full cross-linked in 12 ~ 48 hours, prepares molecular sieve filled solvent resistant composite membrane.
2. the preparation method that a kind of micro porous molecular sieve according to claim 1 fills solvent resistant composite membrane, it is characterised in that: the micropore size of the micro porous molecular sieve used by step 1 is between 0.5～1.0nm.
3. the preparation method that a kind of micro porous molecular sieve according to claim 1 fills solvent resistant composite membrane, it is characterised in that: the silane coupler used by step 1 is trim,ethylchlorosilane, chlorotriethyl silane, butyl Ethoxysilane, octyl group trimethoxy silane or hexadecyl trichlorosilane.
4. the preparation method that a kind of micro porous molecular sieve according to claim 1 fills solvent resistant composite membrane, it is characterised in that: the fluorosilicon oil used by step 2, partial side-chain is γ-trifluoro propyl, to contain part of hydroxyl on hydroxy-end capped or main chain.
5. the preparation method that a kind of micro porous molecular sieve according to claim 1 fills solvent resistant composite membrane, it is characterised in that: fluorosilicon oil used in step 2, the chain hop count wherein containing γ-trifluoro propyl side chain accounts for the 30%-100% of total chain hop count.
6. the preparation method that a kind of micro porous molecular sieve according to claim 1 fills solvent resistant composite membrane, it is characterised in that: cross-linking agent used in step 2 is any one in tetraethyl orthosilicate, octyl group trimethoxy silane, γ aminopropyltriethoxy silane, phenyltrimethoxysila,e, phenyl three TMOS, containing hydrogen silicone oil.
7. the preparation method that a kind of micro porous molecular sieve according to claim 1 fills solvent resistant composite membrane, it is characterized in that: catalyst used in step 2 is organic tin catalyst, and described organic tin catalyst is dibutyl tin laurate or dibutyl dibutyltin diacetate.
8. the preparation method that a kind of micro porous molecular sieve according to claim 1 fills solvent resistant composite membrane, it is characterised in that: organic solvent used in step 1 is toluene, dimethylbenzene or heptane; Organic solvent used in step 2 is acetone, butanone, pentanone, acetyl butyryl, toluene, dimethylbenzene or heptane.
9. the preparation method that a kind of micro porous molecular sieve according to claim 1 fills solvent resistant composite membrane, it is characterised in that: ultrafilter membrane used in step 3 is any one in Kynoar, polyimides, Polyetherimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410652268.3A CN104383819B (en) | 2014-11-17 | 2014-11-17 | The preparation method that a kind of micro porous molecular sieve fills solvent resistant composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410652268.3A CN104383819B (en) | 2014-11-17 | 2014-11-17 | The preparation method that a kind of micro porous molecular sieve fills solvent resistant composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104383819A CN104383819A (en) | 2015-03-04 |
| CN104383819B true CN104383819B (en) | 2016-06-15 |
Family
ID=52601830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410652268.3A Active CN104383819B (en) | 2014-11-17 | 2014-11-17 | The preparation method that a kind of micro porous molecular sieve fills solvent resistant composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104383819B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413499B (en) * | 2015-11-27 | 2017-07-07 | 浙江大学 | A kind of cross-linking modified polyamide composite film and preparation method thereof |
| CN105536568B (en) * | 2015-12-08 | 2018-02-06 | 南京九思高科技有限公司 | A kind of gas separation membrane of resistance to organic steam corrosion and preparation method thereof |
| CN107349797B (en) * | 2016-05-10 | 2020-06-23 | 宁波水艺膜科技发展有限公司 | Super-hydrophilic polymer microporous membrane and manufacturing method thereof |
| CN108176259A (en) * | 2018-01-17 | 2018-06-19 | 浙江工业大学 | A kind of modified polyamide reverse osmosis membrane and its manufacturing method |
| CN111725523A (en) * | 2020-06-04 | 2020-09-29 | 浙江高成绿能科技有限公司 | Thin-layer hydrophobic fuel cell membrane electrode and preparation method thereof |
| CN114146583B (en) * | 2021-11-30 | 2022-12-23 | 中国矿业大学(北京) | Preparation method of MIL-100 (Fe)/PDMS film |
| CN115411292B (en) * | 2022-09-01 | 2023-08-18 | 南京工业大学 | Molecular cross-linked molecular sieve nanosheet hybrid membrane, preparation method and application thereof in flow battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738086A (en) * | 2005-07-19 | 2006-02-22 | 武汉理工大学 | Graft olefin sulfonic acid proton exchange membrane containing hydrogen silicone oil and its preparing method |
| KR100638323B1 (en) * | 2005-05-17 | 2006-10-24 | (주)에어레인 | Silica/porous hollow fiber carbonmolecular sieve membrane for hydrogen gas separation and preparation method thereof |
| CN102061095A (en) * | 2010-11-11 | 2011-05-18 | 暨南大学 | Hybrid film containing fluorosilicone/silicon rubber, and preparation method and application thereof |
| CN102327747A (en) * | 2011-08-01 | 2012-01-25 | 大连理工大学 | Fluorine-containing polysiloxane rubber state composite gas separation membrane, preparation method and application thereof |
-
2014
- 2014-11-17 CN CN201410652268.3A patent/CN104383819B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100638323B1 (en) * | 2005-05-17 | 2006-10-24 | (주)에어레인 | Silica/porous hollow fiber carbonmolecular sieve membrane for hydrogen gas separation and preparation method thereof |
| CN1738086A (en) * | 2005-07-19 | 2006-02-22 | 武汉理工大学 | Graft olefin sulfonic acid proton exchange membrane containing hydrogen silicone oil and its preparing method |
| CN102061095A (en) * | 2010-11-11 | 2011-05-18 | 暨南大学 | Hybrid film containing fluorosilicone/silicon rubber, and preparation method and application thereof |
| CN102327747A (en) * | 2011-08-01 | 2012-01-25 | 大连理工大学 | Fluorine-containing polysiloxane rubber state composite gas separation membrane, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104383819A (en) | 2015-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104383819B (en) | The preparation method that a kind of micro porous molecular sieve fills solvent resistant composite membrane | |
| CN106582317B (en) | A kind of preparation method of the metal organic framework modification graphene oxide layer structure composite film for organic solvent nanofiltration | |
| CN105617994B (en) | A kind of metal-organic framework materials are used for the dyestuff for efficiently separating adjoining dimensions | |
| CN103304177B (en) | Preparation method of modified silicon powder | |
| CN105833811A (en) | Double-capsule self-repairing epoxy coating and preparation method thereof | |
| CN102634062B (en) | Method for preparing high-tenacity reclaimed rubber by adding coupling agent | |
| CN102399566A (en) | Method for extracting heavy liquefied oil and kerite substance from residue of direct coal liquefaction | |
| CN104558614B (en) | Crosslinking agent with MQ unit, preparation method and application thereof | |
| CN106675548A (en) | Self-suspension propping agent and preparation method thereof | |
| CN107042088A (en) | Preparation method for the modified bentonite adsorbent of waste water decoloration of cation dyes | |
| CN104212154B (en) | Sulfonated polyether-ether-ketone-amination silicon dioxide microsphere hybridized film and preparation and application | |
| CN105778525A (en) | Vegetable oil regenerated asphalt and preparation method thereof | |
| CN103212314B (en) | Blended prior-alcohol-permeacomposite composite membrane of a kind of modified ZSM-5 zeolite and preparation method thereof | |
| CN104446043A (en) | Method for preparing high-performance modified mountain powder | |
| CN205235471U (en) | Oil water separator for epoxy | |
| CN108070401A (en) | A kind of separation method of alkylation reaction product | |
| CN202410273U (en) | Washing and filtering integrated device used in preparation of mesocarbon microbeads | |
| CN111482092A (en) | Preparation method of SAPO-34/PDMS gas permeable membrane | |
| CN103834179B (en) | A kind of artificial culture stone mold glue and preparation method thereof | |
| CN106190091A (en) | A kind of waterproofing type proppant of oil thoroughly and preparation method thereof | |
| CN106492658A (en) | A kind of preparation method of doughnut organic gas seperation film | |
| CN104437141A (en) | Preparation method of solvent resistant nanofiltration membrane | |
| CN109181739A (en) | Oil sand separating method | |
| CN104258746B (en) | A kind of preparation method of modified organic silicon dephenolize film | |
| CN203807374U (en) | Production equipment of circulating terpene-phenolic resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |