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
- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 62
- 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 62
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000002904 solvent Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005266 casting Methods 0.000 claims abstract description 18
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 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 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920002545 silicone oil Polymers 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
- 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
- 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
- NZLXTAHHRWZCJR-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(CCC)[Sn](CCCC)(CCCC)CCCC Chemical compound C(C)(=O)O.C(C)(=O)O.C(CCC)[Sn](CCCC)(CCCC)CCCC NZLXTAHHRWZCJR-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
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical group CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008961 swelling Effects 0.000 abstract description 4
- 210000000433 stratum disjunctum Anatomy 0.000 abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 39
- 239000003921 oil Substances 0.000 description 29
- 235000019198 oils Nutrition 0.000 description 28
- 235000012424 soybean oil Nutrition 0.000 description 27
- 239000003549 soybean oil Substances 0.000 description 27
- 230000004907 flux Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000000108 ultra-filtration Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 210000000582 semen Anatomy 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000007788 liquid Substances 0.000 description 4
- 238000001728 nano-filtration Methods 0.000 description 4
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- -1 polydimethylsiloxane Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- 238000004132 cross linking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000013461 design Methods 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
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 235000021251 pulses Nutrition 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000013112 stability test Methods 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000000528 Ricinus communis Species 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
- 230000009471 action Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 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
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process 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
- 238000000605 extraction 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
- 238000009434 installation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000000203 mixture Substances 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
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003204 osmotic effect Effects 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
- 238000004987 plasma desorption mass spectroscopy 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
- 238000007670 refining Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 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 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 | |
| CN103304177B (en) | Preparation method of modified silicon powder | |
| CN105617994B (en) | A kind of metal-organic framework materials are used for the dyestuff for efficiently separating adjoining dimensions | |
| 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 asphalt substances from direct coal liquefaction residues | |
| CN104558614B (en) | Crosslinking agent with MQ unit, preparation method and application thereof | |
| CN106675548A (en) | Self-suspension propping agent 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 | |
| CN206924460U (en) | The purification devices of capsaicine | |
| CN111482092B (en) | Preparation method of SAPO-34/PDMS organic gas permeable membrane | |
| CN103834179B (en) | A kind of artificial culture stone mold glue and preparation method thereof | |
| CN104258746B (en) | A kind of preparation method of modified organic silicon dephenolize film | |
| CN103470951A (en) | Exhaust gas recycling device for gathering tank | |
| CN104437141A (en) | Preparation method of solvent resistant nanofiltration membrane | |
| CN106492658A (en) | A kind of preparation method of doughnut organic gas seperation film | |
| CN106190091A (en) | A kind of waterproofing type proppant of oil thoroughly and preparation method thereof | |
| CN104231271A (en) | Liquid silicon resin and preparation method and application thereof | |
| CN104212153B (en) | Sulfonated polyether-ether-ketone-carboxylic acid silicon dioxide microsphere hybridized film and preparation and application | |
| CN203807374U (en) | Production equipment of circulating terpene-phenolic resin | |
| CN114634802A (en) | Temperature-resistant salt-resistant super-hydrophobic laminating blocking agent and preparation method thereof | |
| CN105819725A (en) | Plant oil regenerated asphalt mixture and preparation method thereof |
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 |