CN104383819A - Preparation method of microporous molecular sieve filled solvent resistant composite film - Google Patents
Preparation method of microporous molecular sieve filled solvent resistant composite film Download PDFInfo
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- CN104383819A CN104383819A CN201410652268.3A CN201410652268A CN104383819A CN 104383819 A CN104383819 A CN 104383819A CN 201410652268 A CN201410652268 A CN 201410652268A CN 104383819 A CN104383819 A CN 104383819A
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- molecular sieve
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- resistant composite
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 239000002904 solvent Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000005266 casting Methods 0.000 claims abstract description 19
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 107
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- -1 dibutyltin dibutyl diacetate Chemical compound 0.000 claims description 4
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical compound CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000012974 tin catalyst Substances 0.000 claims description 4
- RYPYGDUZKOPBEL-UHFFFAOYSA-N trichloro(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl RYPYGDUZKOPBEL-UHFFFAOYSA-N 0.000 claims description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- UZJVTTLANRELSN-UHFFFAOYSA-N butyl(ethoxy)silane Chemical compound CCCC[SiH2]OCC UZJVTTLANRELSN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 30
- 239000000203 mixture Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 77
- 239000003921 oil Substances 0.000 description 56
- 235000019198 oils Nutrition 0.000 description 55
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 39
- 235000012424 soybean oil Nutrition 0.000 description 26
- 239000003549 soybean oil Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 20
- 230000004907 flux Effects 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 14
- 238000002386 leaching Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000012466 permeate Substances 0.000 description 7
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007790 scraping Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001728 nano-filtration Methods 0.000 description 5
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- 244000068988 Glycine max Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000003849 solvent resist ant nanofiltration Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RCHUVCPBWWSUMC-UHFFFAOYSA-N trichloro(octyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)Cl RCHUVCPBWWSUMC-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- MJYQFWSXKFLTAY-OVEQLNGDSA-N (2r,3r)-2,3-bis[(4-hydroxy-3-methoxyphenyl)methyl]butane-1,4-diol;(2r,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O.C1=C(O)C(OC)=CC(C[C@@H](CO)[C@H](CO)CC=2C=C(OC)C(O)=CC=2)=C1 MJYQFWSXKFLTAY-OVEQLNGDSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a microporous molecular sieve filled solvent resistant composite film. The preparation method comprises the following steps: preparing fluorosilicone oil, a microporous molecular sieve, a crosslinking agent, a catalyst and a solvent into a film casting solution, uniformly coating the film casting solution on a base film by using a solvent resistant ultra-filtration film as the base film, further heating to enable the film casting solution to deeply crosslink with the base film after the solvent is evaporated and solidified so as to obtain the microporous molecular sieve filled solvent resistant composite film. Through the composite film prepared by using the method disclosed by the invention, the molecular sieve is uniformly dispersed in a separation layer, and meanwhile, the separation layer is tightly combined with a support layer; the composite film has good swelling resistance in the organic solvent, and is excellent in separation effect and high in stability when being used for recycling low-molecular weight solvent from an oil mixture, and the separation performance can be stably maintained in long-term operation.
Description
Technical Field
The invention relates to the technical field of solvent-resistant composite membranes, in particular to a preparation method of a microporous molecular sieve filled solvent-resistant composite membrane suitable for recovering a low-molecular-weight organic solvent.
Background
In the production field of chemical industry and the like, a large number of separation processes involving vaporization, such as rectification, distillation and the like, are available, and because the latent heat of vaporization is generally high, the energy consumption of the processes is high. Nanofiltration is a membrane separation process that uses pressure as a driving force to separate a solvent from a solution. Nanofiltration is adopted to recover the solvent from the mixed oil, and a large amount of energy can be saved due to no evaporation process.
The current industrial oil production processes mainly comprise a squeezing method and a solvent leaching method. The solvent leaching method comprises three methods of direct leaching, pre-squeezing-leaching, secondary leaching and the like. The direct leaching method is mainly used for low-oil-content oil materials such as soybean, cottonseed, rice bran and the like; the pre-pressing leaching or the secondary leaching is mainly used for high-oil-content oil materials such as castor seeds, peanut kernels, rapeseed, sunflower seeds, flaxseed and the like.
Compared with a squeezing method, the leaching method has the advantages of high oil yield (94-99%), low residual oil rate of dry dregs (0.5-1.5%), capability of obtaining high-quality crude oil and low-denaturation dregs, capability of realizing continuous and automatic production, high production efficiency, low power consumption and low labor intensity. Due to the series of advantages, the oil production by the leaching method is the mainstream process of the current oil production industry, and the application proportion in developed countries is usually more than 90%.
The extraction solvent is hexane or hexane-based solvent oil six, and the vegetable oil/soybean solution obtained by extraction is usually called mixed oil. The vegetable oil content of the mixed oil is generally between 20% and 30%. In order to recover the solution and obtain the crude oil at the same time, the existing process usually adopts an evaporation process, and the energy consumption is huge.
In the last 80 th century, about 700 million tons of hexane were recovered every year by the U.S. grease processing industry, using evaporation. It is estimated that if membrane process is used instead of evaporation recovery, heat energy can be saved by 2.1X 10 per year21J. The soybean oil consumption of Chinese 2012 1281 ten thousand tons and the soybean of China all over the worldThe oil consumption was 4100 million tons, and it was estimated that more than 1 million tons of hexane were recovered. Because a large amount of solvents are required to be recovered in the production of other vegetable oils such as rapeseed oil and the like, the market for recovering the solvents by a membrane method is huge, and the potential energy-saving benefit is very considerable.
In view of this, researchers have conducted research since the 80 s of the last century, but no ideal membrane material has been found so far. Most membrane materials have poor separation performance on mixed oil, high flux but low retention of soybean oil, or high soybean oil retention but low flux, or low flux and soybean oil retention. A small amount of a membrane material having a good separation performance, such as polydimethylsiloxane, has also been found, but it swells seriously in hexane, has poor stability to a mixed oil, and starts to decrease rapidly in separation performance in less than 100 hours of running in a mixed oil, which makes it impossible to apply it industrially.
Therefore, a new technical solution is needed to solve the above problems.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a microporous molecular sieve filled solvent-resistant composite membrane. The prepared solvent-resistant composite membrane has the advantages of good separation performance, swelling resistance, high mechanical strength, stable long-term operation and the like.
In order to solve the technical problems, the preparation method of the microporous molecular sieve filled solvent-resistant composite membrane comprises the following steps:
step 1: molecular sieve pretreatment
Crushing microporous molecular sieve particles to a particle size of less than 2 microns, adding an organic solvent, stirring and dispersing to prepare a suspension, performing ultrasonic dispersion for 1-2 hours, dropwise adding a silane coupling agent into the suspension, wherein the mass of the silane coupling agent is 10-50% of that of the molecular sieve, stirring at room temperature to 80 ℃ for 1-12 hours, filtering, washing and drying to obtain the molecular sieve modified by the silane coupling agent;
step 2: preparation of casting solution
Dissolving fluorosilicone oil in an organic solvent to prepare a solution with the mass concentration of 10-70%, stirring for dissolving, adding the modified molecular sieve, fully stirring, performing ultrasonic dispersion for 1-5 hours, then sequentially adding a cross-linking agent and a catalyst into the solution, wherein the use amounts of the molecular sieve, the cross-linking agent and the catalyst are respectively 5-30%, 3-15% and 2-5% of the mass of the fluorosilicone oil, and uniformly stirring to obtain a casting solution;
and step 3: preparation of composite membranes
And (3) taking a solvent-resistant ultrafiltration membrane as a bottom membrane, uniformly coating the membrane casting solution obtained in the step (2) on the bottom membrane, standing at room temperature to 60 ℃ for a period of time until the solvent is volatilized and primarily cured, and then carrying out heat treatment in an oven at 80-160 ℃ for 12-48 hours to fully crosslink the membrane so as to obtain the molecular sieve filled solvent-resistant composite membrane.
In the preparation method, the micropore diameter of the microporous molecular sieve used in the step 1 is 0.5-1.0 nm, and a molecular sieve of ZSM-5, Silicalite or modern can be selected.
In the preparation method, the silane coupling agent used in the step 1 is trimethylchlorosilane, triethylchlorosilane, butylethoxysilane, octyltrimethoxysilane or hexadecyltrichlorosilane; the hydrolysable group is chlorine, methoxy, ethoxy or acetyl chloride, and the organic functional group is methyl, ethyl, butyl, hexyl, octyl, dodecyl or hexadecyl.
In the preparation method, part of the side chain of the fluorosilicone oil used in the step 2 is gamma-trifluoropropyl, and the end of the fluorosilicone oil is blocked by hydroxyl or the main chain of the fluorosilicone oil contains part of hydroxyl.
In the preparation method, the number of chain segments containing gamma-trifluoropropyl side chains in the fluorosilicone oil used in the step 2 accounts for 30-100% of the total number of the chain segments.
In the preparation method, the cross-linking agent used in the step 2 is any one of ethyl orthosilicate, octyltrimethoxysilane, gamma-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and hydrogen-containing silicone oil.
In the preparation method, the catalyst used in the step 2 is an organic tin catalyst, and the organic tin catalyst is dibutyltin dilaurate or dibutyltin dibutyl diacetate.
In the preparation method, the organic solvent used in the step 1 is toluene, xylene or heptane; the organic solvent used in step 2 is acetone, butanone, pentanone, hexanedione, toluene, xylene or heptane.
In the preparation method, the ultrafiltration membrane used in the step 3 is any one of polyvinylidene fluoride, polyimide and polyetherimide.
The molecular sieve of the composite membrane prepared by the invention is uniformly dispersed in the separation layer, and meanwhile, the separation layer is tightly combined with the support layer, so that the composite membrane has better anti-swelling performance in an organic solvent, and when the composite membrane is used for recovering a low-molecular-weight solvent from mixed oil, the composite membrane has excellent separation effect and strong stability, and the separation performance is kept stable in long-time operation.
Drawings
FIG. 1 is a schematic diagram of the molecular sieve having pores for hexane to pass through and for soybean oil to pass through.
FIG. 2 is a device for testing the separation performance of the composite membrane according to the present invention.
Wherein: 1. the device comprises a pulse damper, 2, a thermometer, 3, a membrane chamber, 4, a pressure gauge, 5, a back pressure valve, 6, a feed liquid tank, 7, a high-pressure metering pump, 8 and a constant temperature controller.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
The specific embodiment of the preparation method of the microporous molecular sieve filled solvent-resistant composite membrane of the invention is as follows:
example 1
ZSM-5 molecular sieve with the silica-alumina ratio of 300 is crushed to the particle size of less than 2 microns, toluene is added to prepare suspension with the mass concentration of 20 percent, the suspension is ultrasonically dispersed for 1 hour, then octyl trichlorosilane with the mass concentration of 10 percent of ZSM-5 is added, and the mixture is stirred for 12 hours at the temperature of 80 ℃. Filtering, washing and drying to obtain the octyl trichlorosilane modified ZSM-5. Dissolving 10 g of gamma-trifluoropropyl fluorosilicone oil with the number of side chain segments accounting for 50% of the total chain segments in 20 g of butanone, adding 2 g of modified ZSM-5, stirring, performing ultrasonic dispersion for 1 hour, sequentially adding 1 g of phenyltrimethoxysilane and 0.3 g of dibutyltin diacetate, uniformly stirring to obtain a membrane casting solution, and scraping the membrane on the membrane by taking a PVDF ultrafiltration membrane as a bottom membrane. After being placed at room temperature for 24 hours, the mixture is heated in an oven at 80 ℃ for 48 hours to be fully crosslinked, and the ZSM-5 molecular sieve filled solvent-resistant composite membrane is prepared.
The prepared composite membrane is used for testing the separation performance of the mixed oil, when the content of the soybean oil in the mixed oil is 26 percent, the feeding temperature is 25 ℃, and the feeding pressure is 2.4 MPa, the permeation flux is 2.5 kg.m-2·h-1The retention rate for soybean oil was 96.2%. When used in the stability test, the separation performance during the test remained stable, as shown in table 1.
Table 1 stability test of solvent-resistant composite membrane filled with microporous molecular sieve
Example 2
ZSM-5 molecular sieve with the silica-alumina ratio of 300 is crushed to the particle size of less than 2 microns, toluene is added to prepare suspension with the mass concentration of 20 percent, the suspension is ultrasonically dispersed for 1 hour, then octyl trimethoxy silane with the mass concentration of 50 percent of ZSM-5 is added, and the mixture is stirred for 1 hour at room temperature. Filtering, washing and drying to obtain the octyl trimethoxy silane modified ZSM-5. 10 g of gamma-trifluoropropyl fluorosilicone oil with the number of side chain segments accounting for 30 percent of the total chain segments is dissolved in 90 g of toluene, 3 g of modified ZSM-5 is added, ultrasonic dispersion is carried out for 2 hours after stirring, 1 g of phenyltrimethoxysilane and 0.2 g of dibutyltin dilaurate are sequentially added, a casting solution is obtained after uniform stirring, and a PVDF ultrafiltration membrane is used as a basement membrane to scrape the membrane on the basement membrane. After being placed at room temperature for 24 hours, the mixture is heated in an oven at 120 ℃ for 12 hours to be fully crosslinked, and the ZSM-5 molecular sieve filled solvent-resistant composite membrane is prepared.
The prepared composite membrane is used for testing the separation performance of the mixed oil, when the content of the soybean oil in the mixed oil is 25 percent, the feeding temperature is 25 ℃, and the feeding pressure is 2.4 MPa, the permeation flux is 8.2 kg.m-2·h-1The retention rate for soybean oil was 96.2%.
Example 3
The silicate-1 molecular sieve is crushed to the particle size of less than 2 microns, toluene is added to prepare a suspension with the mass concentration of 15%, the suspension is ultrasonically dispersed for 2 hours, and then dodecyl trichlorosilane with the mass concentration of 20% of the silicate is added, and the mixture is stirred for 12 hours at 50 ℃. Filtering, washing and drying to obtain the dodecyl trichlorosilane modified silicate-1. Dissolving 14 g of fluorosilicone oil with the chain segment number of the gamma-trifluoropropyl side chain accounting for 50% of the total chain segment number in 6 g of butanone, adding 0.7 g of modified silicate-1, stirring, performing ultrasonic dispersion for 5 hours, sequentially adding 1.5 g of octyl trimethoxy silane and 0.4 g of dibutyltin diacetate, and uniformly stirring to obtain the casting solution. And (3) taking the PVDF ultrafiltration membrane as a bottom membrane, and scraping the membrane on the bottom membrane. After being placed at room temperature for 24 hours, the mixture is heated in an oven at 120 ℃ for 24 hours to be fully crosslinked, and the silicate-1 molecular sieve filled solvent-resistant composite membrane is prepared.
The prepared composite membrane is used for testing the separation performance of the mixed oil, when the content of the soybean oil in the mixed oil is 25 percent, the feeding temperature is 25 ℃, and the feeding pressure is 2.4 MPa, the permeation flux is 3.5 kg.m-2·h-1The retention rate for soybean oil was 96.6%.
Example 4
The silicate-1 molecular sieve is crushed to the particle size of less than 2 microns, toluene is added to prepare a suspension with the mass concentration of 15%, the suspension is ultrasonically dispersed for 2 hours, and then hexadecyl trichlorosilane with the mass concentration of 20% of the silicate is added, and the mixture is stirred for 8 hours at the temperature of 50 ℃. Filtering, washing and drying to obtain the hexadecyl trichlorosilane modified silicate-1. Dissolving 10 g of fluorosilicone oil with the chain segment number of the gamma-trifluoropropyl side chain accounting for 50% of the total chain segment number in 30 g of butanone, adding 1.5 g of modified silicate-1, stirring, performing ultrasonic dispersion for 5 hours, sequentially adding 1 g of octyltrimethoxysilane and 0.3 g of dibutyltin diacetate, and uniformly stirring to obtain the casting solution. And (3) taking the PVDF ultrafiltration membrane as a bottom membrane, and scraping the membrane on the bottom membrane. After being placed at room temperature for 24 hours, the mixture is heated in an oven at 120 ℃ for 36 hours to be fully crosslinked, and the silicate-1 molecular sieve filled solvent-resistant composite membrane is prepared.
The prepared composite membrane is used for testing the separation performance of the mixed oil, when the content of the soybean oil in the mixed oil is 28 percent, the feeding temperature is 25 ℃, and the feeding pressure is 2.4 MPa, the permeation flux is 7.6 kg.m-2·h-1The retention rate for soybean oil was 97.1%.
Example 5
The silicate-1 molecular sieve is crushed to the particle size of less than 2 microns, toluene is added to prepare a suspension with the mass concentration of 15%, the suspension is ultrasonically dispersed for 1 hour, and then dodecyl trichlorosilane and pyridine are added, wherein the mass of the dodecyl trichlorosilane is 20% of that of the silicate, and the mixture is stirred for 12 hours at 50 ℃. Filtering, washing and drying to obtain the dodecyl trichlorosilane modified silicate-1. Dissolving 10 g of fluorosilicone oil with the chain segment number of the gamma-trifluoropropyl side chain accounting for 100 percent of the total chain segment number in 20 g of pentanone, adding 2.0 g of modified silicate-1, stirring, performing ultrasonic dispersion for 4 hours, sequentially adding 1.5 g of ethyl orthosilicate and 0.5 g of dibutyltin diacetate, uniformly stirring to obtain a casting solution, and scraping the membrane on the base membrane by using a PEI ultrafiltration membrane as the base membrane. After being placed at room temperature for 24 hours, the mixture is heated in an oven at 160 ℃ for 12 hours to be fully crosslinked, and the silicate-1 molecular sieve filled solvent-resistant composite membrane is prepared.
The prepared composite membrane is used for testing the separation performance of the mixed oil, when the content of the soybean oil in the mixed oil is 16 percent, the feeding temperature is 25 ℃, and the feeding pressure is 2.5 MPa, the permeation flux is 3.8 kg.m-2·h-1The retention rate for soybean oil was 97.2%.
Example 6
Grinding the modernite molecular sieve to a particle size of less than 2 microns, adding toluene to prepare a suspension with a mass concentration of 20%, ultrasonically dispersing for 1 hour, then adding octyl trimethoxy silane with the mass of 20% of the modernite, and stirring for 8 hours at room temperature. And filtering, washing and drying to obtain the octyl trimethoxy silane modified modelonite. Dissolving 10 g of fluorosilicone oil with the chain segment number of the gamma-trifluoropropyl side chain accounting for 50% of the total chain segment number in 20 g of butanone, adding 3.0 g of modified modernite, stirring, performing ultrasonic dispersion for 4 hours, sequentially adding 0.3 g of hydrogen-containing silicone oil and 0.3 g of dibutyltin diacetate, uniformly stirring to obtain a casting solution, and scraping the membrane on a bottom membrane by taking a PVDF ultrafiltration membrane as the bottom membrane. After being placed at room temperature for 24 hours, the mixture is heated in an oven at 120 ℃ for 48 hours to be fully crosslinked, and the modernite molecular sieve filled solvent-resistant composite membrane is prepared.
The prepared composite membrane is used for testing the separation performance of the mixed oil, when the content of the soybean oil in the mixed oil is 26 percent, the feeding temperature is 25 ℃, and the feeding pressure is 2.5 MPa, the permeation flux is 4.8 kg.m-2·h-1The retention rate for soybean oil was 97.1%.
Comparative example:
dissolving 10 g of fluorosilicone oil with the chain segment number of the gamma-trifluoropropyl side chain accounting for 50% of the total chain segment number in 20 g of butanone, adding 3.0 g of unmodified modernite molecular sieve, stirring, performing ultrasonic dispersion for 4 hours, sequentially adding 0.5 g of hydrogen-containing silicone oil and 0.3 g of dibutyltin diacetate, uniformly stirring to obtain a casting solution, and scraping the membrane on a bottom membrane by taking a PVDF ultrafiltration membrane as the bottom membrane. After being placed at room temperature for 24 hours, the mixture is dried in an oven at 120 ℃ for 48 hours to be fully crosslinked, so that the unmodified modernite molecular sieve filled solvent-resistant composite membrane is prepared.
In the above examples, the prepared fluorosilicone oil solvent-resistant nanofiltration membrane was used for testing the separation performance of mixed oil, and when the soybean oil content in the mixed oil was 25%, the feeding temperature was 25 ℃, and the feeding pressure was 2.5 MPa, the permeation flux was 3.4 kg · m-2·h-1The retention rate for soybean oil was 96.0%. The unmodified modernite molecular sieve has poor dispersion in a fluorosilicone oil separation layer, and hydroxyl on the surface of the molecular sieve has a repulsive effect on hexane, so that the flux and the retention rate are reduced.
In the invention, the gamma-trifluoropropyl is used for partially replacing the original side chain of the fluorosilicone oil, and the gamma-trifluoropropyl can provide a larger shielding effect for the main chain of PDMS due to the repulsion of the gamma-trifluoropropyl to hexane and soybean oil, thereby greatly enhancing the stability of the fluorosilicone oil. The gamma-trifluoropropyl is called as fluorosilicone oil after partially or completely replacing the side chain group of the silicon rubber, and when the end of the fluoro-silicone oil is terminated by hydroxyl and the side chain is the gamma-trifluoropropyl and the methyl, the molecular structural formula is as follows:；
the molecular structural formula of the end-capped organic group with the side chain of gamma-trifluoropropyl, methyl and hydroxyl is shown as the following formula:。
in the pretreatment of the molecular sieve, the molecular sieve is a substance having uniform micropores and a pore size equivalent to the size of a general molecule. The common molecular sieve is crystalline silicate or aluminosilicate, which is a pore and cavity system formed by connecting silicon-oxygen tetrahedron or aluminum-oxygen tetrahedron through oxygen bridge bond, and has the capability of sieving fluid molecules with different sizes due to different sizes and shapes of adsorbed molecules.
In the preparation of the casting solution, the molecular sieve is filled in the fluorosilicone oil, and has two functions:
1. promoting the cross-linking of the fluorosilicone oil and increasing the action between the fluorosilicone oil and the molecular sieve, thereby greatly increasing the cross-linking degree, toughness and stability of the composite membrane;
2. as shown in fig. 1, if the pore channels of the molecular sieve allow hexane to pass smoothly and block the soybean oil from passing, hexane permeation is promoted, and the soybean oil has a reduced flux due to a longer mass transfer path.
The surface of the molecular sieve generally has hydrophilic groups, so that the molecular sieve can not be well dispersed in a membrane casting solution, and local defects of the composite membrane can be easily caused in places with serious agglomeration. Therefore, the molecular sieve is subjected to certain hydrophobic modification before use, so that the dispersibility of the molecular sieve in the casting solution can be improved.
Referring to fig. 2, the apparatus for testing the separation performance of the composite membrane absorbs hexane from a soybean oil/hexane mixed oil in a nanofiltration manner.
FIG. 2 is a testing device for separation performance of composite membrane, wherein a thermometer 2 and a pressure gauge 4 are respectively arranged on an input pipeline and an output pipeline of a membrane chamber 3, a back pressure valve 5 is arranged on a pipeline of the membrane chamber 3 leading to a feed liquid tank 6, an output pipeline at the bottom of the feed liquid tank 6 is connected with a high-pressure metering pump 7, a pulse damper 1 is arranged on the high-pressure metering pump 7, and a constant temperature range is adjusted by a constant temperature controller 8.
The mixed oil with certain temperature and certain concentration flows through the surface of the composite membrane under certain pressure, under the action of the pressure, the solvent and a small amount of soybean oil overcome osmotic pressure and permeate the composite membrane to obtain penetrating fluid with low oil content, and the concentrated solution returns to the feed liquid tank for continuous circulation.
The composite membrane is used for nanofiltration, and the separation performance of the composite membrane mainly has two indexes, namely flux and selectivity.
1) Composite membrane permeate flux, which is used to characterize the rate at which a permeate component permeates through a membrane, is the amount of a mixture component that diffuses through the membrane per unit area of time and is defined by the formula:
wherein,Jmeans the flux of permeation: (）；MThe mass of the permeate liquid: (kg）；AIs an effective membrane area: (m 2 ）；tFor the operating time (h）。
2) The retention rate represents the separation effect of the nanofiltration membrane on hexane and soybean oil, and is defined by the following formula:
wherein,c fis the concentration of oil in the feed solution,c pis the concentration of oil in the permeate. Retention rateRBetween 0 and 100% of the total amount of the composition,Rthe larger the size, the less soybean oil in the permeate, the better the separation effect.
The stability is another important index for evaluating the composite membrane, and whether the composite membrane can stably run for a long time is the key for realizing industrialization of the composite membrane in a certain system.
The solvent-resistant nanofiltration membrane prepared by the invention has the permeation flux of 5.3 kg.m-2·h-1The retention rate can reach 98.5%, and the penetrating fluid can be directly reused for leaching the vegetable oil. More importantly, the solvent-resistant nanofiltration membrane prepared by the method has good stability, the separation performance is kept stable in long-term operation, and the method has great industrial application potential.
Claims (9)
1. A preparation method of a microporous molecular sieve filled solvent-resistant composite membrane is characterized by comprising the following steps:
step 1: molecular sieve pretreatment
Crushing microporous molecular sieve particles to a particle size of less than 2 microns, adding an organic solvent, stirring and dispersing to prepare a suspension, performing ultrasonic dispersion for 1-2 hours, dropwise adding a silane coupling agent into the suspension, wherein the mass of the silane coupling agent is 10-50% of that of the molecular sieve, stirring at room temperature to 80 ℃ for 1-12 hours, filtering, washing and drying to obtain the molecular sieve modified by the silane coupling agent;
step 2: preparation of casting solution
Dissolving fluorosilicone oil in an organic solvent to prepare a solution with the mass concentration of 10-70%, stirring for dissolving, adding the modified molecular sieve, fully stirring, performing ultrasonic dispersion for 1-5 hours, then sequentially adding a cross-linking agent and a catalyst into the solution, wherein the use amounts of the molecular sieve, the cross-linking agent and the catalyst are respectively 5-30%, 3-15% and 2-5% of the mass of the fluorosilicone oil, and uniformly stirring to obtain a casting solution;
and step 3: preparation of composite membranes
And (3) taking a solvent-resistant ultrafiltration membrane as a bottom membrane, uniformly coating the membrane casting solution obtained in the step (2) on the bottom membrane, standing at room temperature to 60 ℃ for a period of time until the solvent is volatilized and primarily cured, and then carrying out heat treatment in an oven at 80-160 ℃ for 12-48 hours to fully crosslink the membrane so as to obtain the molecular sieve filled solvent-resistant composite membrane.
2. The method of claim 1, wherein the microporous molecular sieve filled solvent-resistant composite membrane is prepared by a method comprising the steps of: the micropore diameter of the microporous molecular sieve used in the step 1 is 0.5-1.0 nm.
3. The method of claim 1, wherein the microporous molecular sieve filled solvent-resistant composite membrane is prepared by a method comprising the steps of: the silane coupling agent used in the step 1 is trimethylchlorosilane, triethylchlorosilane, butylethoxysilane, octyltrimethoxysilane or hexadecyltrichlorosilane.
4. The method of claim 1, wherein the microporous molecular sieve filled solvent-resistant composite membrane is prepared by a method comprising the steps of: and (3) part of the side chains of the fluorosilicone oil used in the step 2 are gamma-trifluoropropyl, and the fluorosilicone oil is terminated by hydroxyl or contains part of hydroxyl on the main chain.
5. The method of claim 1, wherein the microporous molecular sieve filled solvent-resistant composite membrane is prepared by a method comprising the steps of: the fluorosilicone oil used in the step 2 has chain segments containing gamma-trifluoropropyl side chains accounting for 30-100% of the total number of the chain segments.
6. The method of claim 1, wherein the microporous molecular sieve filled solvent-resistant composite membrane is prepared by a method comprising the steps of: the cross-linking agent used in the step 2 is any one of ethyl orthosilicate, octyltrimethoxysilane, gamma-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and hydrogen-containing silicone oil.
7. The method of claim 1, wherein the microporous molecular sieve filled solvent-resistant composite membrane is prepared by a method comprising the steps of: the catalyst used in the step 2 is an organic tin catalyst, and the organic tin catalyst is dibutyltin dilaurate or dibutyltin dibutyl diacetate.
8. The method of claim 1, wherein the microporous molecular sieve filled solvent-resistant composite membrane is prepared by a method comprising the steps of: the organic solvent used in the step 1 is toluene, xylene or heptane; the organic solvent used in step 2 is acetone, butanone, pentanone, hexanedione, toluene, xylene or heptane.
9. The method of claim 1, wherein the microporous molecular sieve filled solvent-resistant composite membrane is prepared by a method comprising the steps of: the ultrafiltration membrane used in the step 3 is any one of polyvinylidene fluoride, polyimide and polyetherimide.
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