CN116262210B - High-selectivity pervaporation gasoline desulfurization membrane and preparation method thereof - Google Patents
High-selectivity pervaporation gasoline desulfurization membrane and preparation method thereof Download PDFInfo
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- CN116262210B CN116262210B CN202111519413.7A CN202111519413A CN116262210B CN 116262210 B CN116262210 B CN 116262210B CN 202111519413 A CN202111519413 A CN 202111519413A CN 116262210 B CN116262210 B CN 116262210B
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- triethoxysilylpropyl
- gamma
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- pervaporation
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 51
- 230000023556 desulfurization Effects 0.000 title claims abstract description 51
- 238000005373 pervaporation Methods 0.000 title claims abstract description 51
- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 61
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 61
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 57
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 claims abstract description 32
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000007062 hydrolysis Effects 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 230000004907 flux Effects 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- 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 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052961 molybdenite Inorganic materials 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 20
- 229930192474 thiophene Natural products 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 86
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 47
- 239000012065 filter cake Substances 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 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 4
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002954 polymerization reaction product Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical class CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/11—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by dialysis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application relates to a high-selectivity pervaporation gasoline desulfurization membrane and a preparation method thereof, wherein bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide is used as a framework structure raw material, and hydrolysis polymerization reaction is carried out in a mixed solvent of ethanol and water under the catalysis of nitric acid, so that an organic silica sol with a framework structure is obtained. The framework structure contains a large number of disulfide bonds (-S-S-) or tetrasulfide bonds (-S-S-S-S-) as bridging chains of the framework, has good affinity to thiophene, and can remarkably increase the selectivity of the membrane to thiophene molecules. In the hydrolysis polymerization process, the filler nano particles are further matched to form partial coating, and then the partial coating is mutually crosslinked with hydroxyl-terminated polydimethylsiloxane and polydimethylsiloxane to form a film, so that the high-selectivity pervaporation gasoline desulfurization film is obtained, and the permeation flux of the pervaporation gasoline desulfurization film can reach 12.56Kg/m 2 * h, and the sulfur-rich factor can reach 8.69.
Description
Technical Field
The application relates to the technical field of membrane separation, in particular to a high-selectivity pervaporation gasoline desulfurization membrane and a preparation method thereof.
Background
Gasoline is one of the most important energy sources in industrial society, and at the same time, sulfur in gasoline is also the most direct source of various sulfur oxides in air. With the increasing importance of global environmental protection, the reduction of environmental pollution caused by sulfur oxides, and the production of clean gasoline with ultra-low sulfur content has become an important topic worldwide.
The traditional gasoline desulfurization process is a hydrodesulfurization process. Although hydrodesulfurization can effectively remove sulfides which are difficult to remove, such as thiophene, the technology has high cost, strict operating conditions and more octane number loss. The organic sulfide is converted into hydrogen sulfide after being hydrotreated, and the hydrogen sulfide can be recovered and discharged only through a complex tail gas treatment process, so that the process is complicated.
The membrane separation technology is a new chemical separation technology, the pervaporation is a physical gasoline desulfurization technology, does not involve chemical reaction, does not generate harmful byproducts, and has the advantages of environmental friendliness, low cost, low octane number loss and the like.
The core of the pervaporation technology is a pervaporation membrane material, mainly a polymer membrane material, comprising polydimethylsiloxane PDMS, polyethylene glycol PEG, ethylcellulose EC, polyether block amide PEBAX, polyurethane PU, polyimide PI and the like.
Among them, polydimethylsiloxane PDMS has very strong permeability, especially suitable for the industrial large-scale osmotic separation production. However, in the pervaporation desulfurization process of gasoline, the selectivity of polydimethylsiloxane to thiophene, a main sulfide in the gasoline, is low, the desulfurization effect is poor, and the swelling resistance of polydimethylsiloxane is also poor, so that the industrial application of polydimethylsiloxane is also a certain obstacle. Therefore, in order to obtain a better desulfurization effect, the polydimethylsiloxane membrane needs to be modified to provide a high-selectivity pervaporation gasoline desulfurization membrane.
Disclosure of Invention
In order to solve the problems of low selectivity and poor swelling resistance of the existing pervaporation gasoline desulfurization membrane, the application takes a polydimethylsiloxane material as a basis to modify the membrane, improves sulfur-rich factors and enhances swelling resistance and mechanical properties while not affecting the permeation flux of the membrane.
In a first aspect, the present application relates to a method for preparing a first high selectivity pervaporation gasoline desulfurization membrane, comprising the steps of:
(1) Adding bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide into a mixed solvent of absolute ethyl alcohol and deionized water, wherein the mass ratio of the absolute ethyl alcohol to the deionized water is (3-5): 1, obtaining an organosilicon solution A1 with the concentration of 0.4-1mol/L, and reacting for 4-8 hours under the catalysis of nitric acid at the temperature of 35-45 ℃ to enable the bis- (gamma-triethoxysilylpropyl) tetrasulfide or the bis- (gamma-triethoxysilylpropyl) disulfide to undergo hydrolytic polymerization reaction to obtain a sol solution B1;
(2) 10-20g of hydroxyl-terminated polydimethylsiloxane and 15-25g of polydimethylsiloxane are dissolved in 100g of organic solvent, and then 0.5g of organotin catalyst is added to obtain solution C;
(3) Mixing the sol solution B1 and the solution C according to the volume ratio of (3-8), and ultrasonically stirring to obtain uniform casting solution;
(4) After static defoaming, the casting film liquid is coated on the surface of a ZrO2/Al2O3 support body, the coating thickness is 15-35um, the casting film liquid is dried in an oven at the temperature of 110-120 ℃ for 8-12h, and is crosslinked to form a film, so that a hydrolysis polymerization product of bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide, hydroxyl-terminated polydimethylsiloxane and polydimethylsiloxane are mutually crosslinked to form a film, and finally the pervaporation gasoline desulfurization film is obtained.
In the first preparation method of the pervaporation gasoline desulfurization membrane, the organic solvent is one of hexane, heptane and octane; the organotin catalyst is dibutyl tin dilaurate; the amount of nitric acid is 1-3wt.% of bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide;
the ultrasonic stirring time is 15-45min.
Preferably, the viscosity of the hydroxyl-terminated polydimethylsiloxane is from about 1 pa.s to about 5 pa.s. The viscosity of the polydimethylsiloxane is 10-40 Pa.s.
In the first preparation method of the high-selectivity pervaporation gasoline desulfurization membrane, bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide is used as a framework structure raw material, and hydrolysis polymerization reaction is carried out in a mixed solvent of ethanol and water under the catalysis of nitric acid, so that the organic silica sol with a framework structure is obtained. The framework structure contains a large number of disulfide bonds (-S-S-) or tetrasulfide bonds (-S-S-S-S-) as bridging chains of the framework, has good affinity to thiophene, and can remarkably increase the selectivity of the membrane to thiophene molecules.
In addition, after the sol solution B1 containing disulfide bonds or tetrasulfide bonds, hydroxyl-terminated polydimethylsiloxane and polydimethylsiloxane are crosslinked to form a film, the framework structure containing disulfide bonds or tetrasulfide bonds is crosslinked with the polydimethylsiloxane. The disulfide bond and the tetrasulfide bond have stronger space structure stability, so that the stability of the space structure of the crosslinking molecule can be effectively improved, and the swelling resistance of the PDMS film is further improved.
In a second aspect, the present application also provides a first high-selectivity pervaporation gasoline desulfurization membrane, wherein the permeation flux of the pervaporation gasoline desulfurization membrane is more than or equal to 9.65Kg/m 2 * h, and the sulfur-rich factor is more than or equal to 7.56.
Most preferably, a high selectivity pervaporation gasoline desulfurization membrane having a permeation flux of 11.02Kg/m 2 * h, and the sulfur-rich factor is 8.36.
In a third aspect, the present application relates to a method for preparing a second high selectivity pervaporation gasoline desulfurization membrane, comprising the steps of:
(1) Adding bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide into an absolute ethyl alcohol solvent to obtain an organosilicon solution A2 with the concentration of 0.2-0.6mol/L, dispersing a filler into a deionized water solvent to obtain a dispersion solution D with the concentration of 0.1-0.3mol/L, mixing and stirring the organosilicon solution A2 and the dispersion solution D uniformly according to the volume ratio of 1:1, reacting for 4-8 hours at the temperature of 35-45 ℃ under the catalysis of nitric acid, so that the bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide undergoes hydrolytic polymerization, and coating part of the organosilicon solution A2 on the surface of filler nano particles to obtain a sol solution B2;
(2) 10-20g of hydroxyl-terminated polydimethylsiloxane and 15-25g of polydimethylsiloxane are dissolved in 100g of organic solvent, and then 0.5g of organotin catalyst is added to obtain solution C;
(3) Mixing the sol solution B2 and the solution C according to the volume ratio of (3-8), and ultrasonically stirring to obtain uniform casting solution;
(4) After static defoaming, the casting film liquid is coated on the surface of a ZrO2/Al2O3 support body, the coating thickness is 15-35um, the casting film liquid is dried in an oven at the temperature of 110-120 ℃ for 8-12h, and is crosslinked to form a film, so that a hydrolysis polymerization product of bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide, hydroxyl-terminated polydimethylsiloxane and polydimethylsiloxane are mutually crosslinked to form a film, and finally the pervaporation gasoline desulfurization film is obtained.
In the second method for preparing the pervaporation gasoline desulfurization membrane, the organic solvent is one of hexane, heptane and octane; the organotin catalyst is dibutyl tin dilaurate; the amount of nitric acid is 1-3wt.% of bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide;
the ultrasonic stirring time is 15-45min; the filler is selected from CPO-27-Ni nano particles and Cu 2+ One or more of loaded UiO-67bpydc nano particles and MoS2 nano sheets.
Preferably, the viscosity of the hydroxyl-terminated polydimethylsiloxane is from about 1 pa.s to about 5 pa.s. The viscosity of the polydimethylsiloxane is 10-40 Pa.s.
Preferably, the CPO-27-Ni nanoparticle can be prepared by the following preparation method:
preparing 0.2mol/L nickel acetate aqueous solution and 0.1 mol/L2, 5-dihydroxyterephthalic acid tetrahydrofuran solution; the volume ratio of the two solutions is 1:1, uniformly mixing and stirring, and then carrying out hydrothermal reaction for 24-48 hours at 110-120 ℃ to obtain a yellowish green solution; and (3) washing the yellow-green solution with deionized water, filtering to obtain a filter cake, drying the filter cake at 110-120 ℃ for 4-10 hours, and grinding and sieving to obtain the corresponding CPO-27-Ni nano particles.
Preferably, the Cu 2+ The supported UIO-67bpydc nano particles can be prepared by the following preparation method:
respectively preparing acetonitrile solutions of copper nitrate and UIO-67bpydc with the concentration of 0.5mol/L by calculating copper and zirconium, and mixing the two solutions according to the volume ratio of 1:1, uniformly mixing and stirring, and then carrying out hydrothermal reaction for 12-24 hours at 60-70 ℃; then washing with deionized water, filtering to obtain a filter cake, and drying the filter cake at 110-120 ℃ for 4-8h; then grinding and sieving to obtain corresponding Cu 2+ Loaded UiO-67bpydc nanoparticles.
In the second method for preparing the pervaporation gasoline desulfurization membrane, the hydrolysis reaction of bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide is carried out in a dispersion solvent of filler nanoparticles. The hydrolysis polymerization reaction product can be partially coated on the surface of the filler nano particle, so that the permeability of the membrane is improved, and meanwhile, the structural stability of the membrane is improved by utilizing the mutual coordination of a coating structure, a frame structure and a bridging structure.
In a fourth aspect, the present application also provides a second high-selectivity pervaporation gasoline desulfurization membrane, wherein the permeation flux of the pervaporation gasoline desulfurization membrane is more than or equal to 12.15Kg/m 2 * h, and the sulfur-rich factor is more than or equal to 8.33.
Most preferably, a high selectivity pervaporation gasoline desulfurization membrane having a permeation flux of 12.56Kg/m 2 * h, and the sulfur-rich factor is 8.69.
The beneficial effects are that:
1. the preparation method takes bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide as a framework structure raw material, and the hydrolysis polymerization reaction is carried out in a mixed solvent of ethanol and water under the catalysis of nitric acid, so that the organic silica sol with a framework structure is obtained. The framework structure contains a large number of disulfide bonds (-S-S-) or tetrasulfide bonds (-S-S-S-S-) as bridging chains of the framework, has good affinity to thiophene, and can remarkably increase the selectivity of the membrane to thiophene molecules.
2. The hydrolysis reaction of bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide is carried out in a dispersion solvent of the filler nanoparticles. The hydrolysis polymerization reaction product can be partially coated on the surface of the filler nano particle, so that the permeability of the membrane is improved, and meanwhile, the structural stability of the membrane is improved by utilizing the mutual coordination of a coating structure, a frame structure and a bridging structure.
3. After the sol solution B1 containing disulfide bonds or tetrasulfide bonds, hydroxyl-terminated polydimethylsiloxane and polydimethylsiloxane are crosslinked to form a film, the framework structure containing disulfide bonds or tetrasulfide bonds is crosslinked with polydimethylsiloxane. The disulfide bond and the tetrasulfide bond have stronger space structure stability, so that the stability of the space structure of the crosslinking molecule can be effectively improved, and the swelling resistance of the PDMS film is further improved.
Detailed Description
The following detailed description of the present application is provided in connection with specific embodiments thereof in order to more clearly and specifically describe the features and advantages of the present application.
Example 1
Example 1-1
The preparation method of the high-selectivity pervaporation gasoline desulfurization membrane comprises the following steps:
(1) Adding bis- (gamma-triethoxysilylpropyl) disulfide into a mixed solvent of absolute ethyl alcohol and deionized water, wherein the mass ratio of the absolute ethyl alcohol to the deionized water is 4:1, obtaining an organosilicon solution A1 with the concentration of 0.8mol/L, reacting for 6 hours under the catalysis of nitric acid at 40 ℃, wherein the dosage of the nitric acid is 3wt.% of the bis- (gamma-triethoxysilylpropyl) disulfide, and enabling the bis- (gamma-triethoxysilylpropyl) disulfide to undergo hydrolytic polymerization reaction to obtain a sol solution B1;
(2) 10g of hydroxyl-terminated polydimethylsiloxane (viscosity of about 4 Pa.s) and 25g of polydimethylsiloxane (viscosity of about 25 Pa.s) are dissolved in 100g of octane, and 0.5g of dibutyltin dilaurate catalyst is added to obtain a solution C;
(3) Mixing the sol solution B1 and the solution C according to the volume ratio of 1:5, and ultrasonically stirring for 35min to obtain uniform casting solution;
(4) After static defoaming, the casting solution is coated on the surface of a ZrO2/Al2O3 support body, the coating thickness is about 28 mu m, and the casting solution is dried in an oven at 110 ℃ for 10 hours and crosslinked to form a film, so that the hydrolysis polymerization product of the bis- (gamma-triethoxysilylpropyl) disulfide, the hydroxyl-terminated polydimethylsiloxane and the polydimethylsiloxane are crosslinked to form a film, and finally the pervaporation gasoline desulfurization film is obtained.
Examples 1 to 2
The only difference from example 1-1 is that sol solution B1 and solution C are mixed in a volume ratio of 1:3.
Examples 1 to 3
The only difference from example 1-1 is that sol solution B1 and solution C are mixed in a volume ratio of 1:8.
Example 2
Example 2-1
The preparation method of the high-selectivity pervaporation gasoline desulfurization membrane comprises the following steps:
(1) Adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into a mixed solvent of absolute ethyl alcohol and deionized water, wherein the mass ratio of the absolute ethyl alcohol to the deionized water is 4:1, obtaining an organosilicon solution A1 with the concentration of 0.6mol/L, and reacting for 8 hours at 40 ℃ under the catalysis of nitric acid, wherein the use amount of the nitric acid is 2wt.% of the bis- (gamma-triethoxysilylpropyl) tetrasulfide, so that the bis- (gamma-triethoxysilylpropyl) tetrasulfide undergoes hydrolytic polymerization reaction to obtain a sol solution B1;
(2) 15g of hydroxyl-terminated polydimethylsiloxane (viscosity of about 4 Pa.s) and 20g of polydimethylsiloxane (viscosity of about 20 Pa.s) were dissolved in 100g of heptane, and 0.5g of dibutyltin dilaurate catalyst was added to obtain a solution C;
(3) Mixing the sol solution B1 and the solution C according to the volume ratio of 1:5, and ultrasonically stirring for 45min to obtain uniform casting solution;
(4) After static defoaming, the casting solution is coated on the surface of a ZrO2/Al2O3 support body, the coating thickness is about 28 mu m, and the casting solution is dried in an oven at 110 ℃ for 10 hours and crosslinked to form a film, so that the hydrolysis polymerization product of the bis- (gamma-triethoxysilylpropyl) tetrasulfide, the hydroxyl-terminated polydimethylsiloxane and the polydimethylsiloxane are crosslinked to form a film, and finally the pervaporation gasoline desulfurization film is obtained.
Example 2-2
The only difference from example 2-1 is that sol solution B1 and solution C are mixed in a volume ratio of 1:3.
Examples 2 to 3
The only difference from example 2-1 is that sol solution B1 and solution C are mixed in a volume ratio of 1:8.
Example 3
Preparation of filler:
the filler used in this example was CPO-27-Ni nanoparticles prepared by the following method:
preparing 0.2mol/L nickel acetate aqueous solution and 0.1 mol/L2, 5-dihydroxyterephthalic acid tetrahydrofuran solution; the volume ratio of the two solutions is 1:1, uniformly mixing and stirring, and then carrying out hydrothermal reaction for 40 hours at 120 ℃ to obtain a yellowish green solution; and (3) washing the yellow-green solution with deionized water, filtering to obtain a filter cake, drying the filter cake at 120 ℃ for 8 hours, and grinding and sieving to obtain the corresponding CPO-27-Ni nano particles. The average particle size of CPO-27-Ni nanoparticles was measured to be about 118nm.
Example 3-1
The preparation of the high-selectivity pervaporation gasoline desulfurization membrane comprises the following steps:
(1) Adding bis- (gamma-triethoxysilylpropyl) disulfide into an absolute ethanol solvent to obtain an organosilicon solution A2 with the concentration of 0.4mol/L, dispersing a filler into a deionized water solvent to obtain a dispersion solution D with the concentration of 0.1mol/L, uniformly mixing and stirring the organosilicon solution A2 and the dispersion solution D according to the volume ratio of 1:1, reacting for 8 hours under the catalysis of nitric acid at 35 ℃, wherein the use amount of the nitric acid is 2wt.% of the bis- (gamma-triethoxysilylpropyl) disulfide, so that the bis- (gamma-triethoxysilylpropyl) disulfide undergoes hydrolytic polymerization reaction, and partially coats the surface of filler nano particles to obtain a sol solution B2;
(2) 15g of hydroxy-terminated polydimethylsiloxane and 23g of polydimethylsiloxane were dissolved in 100g of octane, and 0.5g of dibutyltin dilaurate was added to obtain solution C;
(3) Mixing the sol solution B2 and the solution C according to the volume ratio of 1:5, and ultrasonically stirring to obtain uniform casting solution;
(4) After static defoaming, the casting solution is coated on the surface of a ZrO2/Al2O3 support body, the coating thickness is 30 mu m, and the casting solution is dried in an oven at 120 ℃ for 8 hours and crosslinked to form a film, so that the hydrolysis polymerization product of the bis- (gamma-triethoxysilylpropyl) disulfide, the hydroxyl-terminated polydimethylsiloxane and the polydimethylsiloxane are crosslinked to form a film, and finally the pervaporation gasoline desulfurization film is obtained.
Example 3-2
The only difference from example 3-1 is that sol solution B1 and solution C are mixed in a volume ratio of 1:3.
Examples 3 to 3
The only difference from example 3-1 is that sol solution B1 and solution C are mixed in a volume ratio of 1:8.
Example 4
Preparation of filler:
the filler used in this example was Cu 2+ The loaded UIO-67bpydc nano-particles are prepared by the following preparation method:
respectively preparing acetonitrile solutions of copper nitrate and UIO-67bpydc with the concentration of 0.5mol/L by calculating copper and zirconium, and mixing the two solutions according to the volume ratio of 1:1, uniformly mixing and stirring, and then carrying out hydrothermal reaction for 20 hours at 60 ℃; then washing with deionized water, filtering to obtain a filter cake, and drying the filter cake at 110 ℃ for 7 hours; then grinding and sieving to obtain corresponding Cu 2+ Loaded UiO-67bpydc nanoparticles. The average particle size of CPO-27-Ni nanoparticles was found to be about 133nm.
Example 4-1
The preparation of the high-selectivity pervaporation gasoline desulfurization membrane comprises the following steps:
(1) Adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an absolute ethyl alcohol solvent to obtain an organosilicon solution A2 with the concentration of 0.6mol/L, dispersing a filler into a deionized water solvent to obtain a dispersion solution D with the concentration of 0.2mol/L, uniformly mixing and stirring the organosilicon solution A2 and the dispersion solution D according to the volume ratio of 1:1, and reacting for 8 hours at 42 ℃ under the catalysis of nitric acid, wherein the use amount of the nitric acid is 2wt.% of the bis- (gamma-triethoxysilylpropyl) tetrasulfide, so that the bis- (gamma-triethoxysilylpropyl) tetrasulfide undergoes hydrolytic polymerization reaction, and the filler nanoparticle surface is partially coated with the filler to obtain a sol solution B2;
(2) 18g of hydroxy-terminated polydimethylsiloxane and 22g of polydimethylsiloxane were dissolved in 100g of octane, and 0.5g of dibutyltin dilaurate was added to obtain solution C;
(3) Mixing the sol solution B2 and the solution C according to the volume ratio of 1:5, and ultrasonically stirring to obtain uniform casting solution;
(4) After static defoaming, the casting solution is coated on the surface of a ZrO2/Al2O3 support body, the coating thickness is 27 mu m, and the casting solution is dried in an oven at 115 ℃ for 11 hours and crosslinked to form a film, so that the hydrolysis polymerization product of the bis- (gamma-triethoxysilylpropyl) tetrasulfide, the hydroxyl-terminated polydimethylsiloxane and the polydimethylsiloxane are crosslinked to form a film, and finally the pervaporation gasoline desulfurization film is obtained.
Example 4-2
The only difference from example 4-1 is that sol solution B1 and solution C are mixed in a volume ratio of 1:3.
Examples 4 to 3
The only difference from example 4-1 is that sol solution B1 and solution C are mixed in a volume ratio of 1:8.
Comparative example 1
The difference compared to example 1-1 is only the substitution of 1, 2-bis trimethoxysilylethane for bis- (gamma-triethoxysilylpropyl) disulfide.
Comparative example 2
The difference compared to example 3-1 is only the substitution of 1, 2-bis trimethoxysilylethane for bis- (gamma-triethoxysilylpropyl) disulfide.
Performance testing
(1) The simulated pervaporation desulfurization test was performed at 45℃using a simulated reagent of octane gasoline solution containing 200ppm thiophene. The test duration of the pervaporation performance is 5 hours, the absolute pressure of the film thickness is 200Pa, and the effective film area is about 3.52cm 2 . The permeation fluxes and sulfur-rich factors of the respective membranes of example 1 to example 4 and comparative example 1 were measured, and the specific results are shown in Table 1.
TABLE 1
As can be seen from table 1, the high selectivity pervaporation gasoline desulfurization membrane of the present application has excellent permeation flux and sulfur-rich factor. With the increase of the hydrolytic polymerization products of bis- (gamma-triethoxysilylpropyl) disulfide or bis- (gamma-triethoxysilylpropyl) tetrasulfide, both the permeation flux of the membrane and the sulfur-rich factor show an increasing trend. The hydrolysis polymerization product prepared in the step (1) is used for crosslinking with hydroxyl-terminated polydimethylsiloxane and polydimethylsiloxane to form a film, so that the permeation flux and the sulfur-rich factor of the film are well improved.
(2) Swelling Performance test
The simulated permeation desulfurization test was conducted at 45℃using octane gasoline solutions containing 100ppm, 200ppm, 400ppm, 600ppm, 800ppm, 1000ppm, 1500ppm, 2000ppm of thiophene, respectively. The test duration of the pervaporation performance is 2 hours, the absolute pressure of the film thickness is 200Pa, and the effective film area is about 3.52cm 2 . The swelling ratios of the two films of example 1-1 and comparative example 1 were measured, and the specific results are shown in Table 2.
TABLE 2
As can be seen from table 2, the pervaporation gasoline desulfurization membrane of the present application has excellent swelling resistance.
Claims (9)
1. The preparation method of the high-selectivity pervaporation gasoline desulfurization membrane comprises the following steps: (1) Adding bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide into a mixed solvent of absolute ethyl alcohol and deionized water, wherein the mass ratio of the absolute ethyl alcohol to the deionized water is (3-5): 1, obtaining an organosilicon solution A1 with the concentration of 0.4-1mol/L, and reacting for 4-8 hours under the catalysis of nitric acid at the temperature of 35-45 ℃ to enable the bis- (gamma-triethoxysilylpropyl) tetrasulfide or the bis- (gamma-triethoxysilylpropyl) disulfide to undergo hydrolytic polymerization reaction to obtain a sol solution B1;
(2) 10-20g of hydroxyl-terminated polydimethylsiloxane and 15-25g of polydimethylsiloxane are dissolved in 100g of organic solvent, and then 0.5g of organotin catalyst is added to obtain solution C;
(3) Mixing the sol solution B1 and the solution C according to the volume ratio of (3-8), and ultrasonically stirring to obtain uniform casting solution;
(4) Coating the casting solution on the surface of a ZrO2/Al2O3 support body after static defoaming, wherein the coating thickness is 15-35 mu m, drying in an oven at 110-120 ℃ for 8-12h, and crosslinking to form a film, so that a hydrolysis polymerization product of bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide, hydroxyl-terminated polydimethylsiloxane and polydimethylsiloxane are mutually crosslinked to form a film, and finally the pervaporation gasoline desulfurization film is obtained.
2. The method for preparing a high-selectivity pervaporation gasoline desulfurization membrane according to claim 1, wherein the organic solvent is one of hexane, heptane and octane; the organotin catalyst is dibutyl tin dilaurate; the amount of nitric acid is 1-3wt.% of bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide; the ultrasonic stirring time is 15-45min.
3. The method for preparing a high-selectivity pervaporation gasoline desulfurization membrane according to claim 1, wherein the viscosity of the hydroxyl-terminated polydimethylsiloxane is 1-5pa·s; the viscosity of the polydimethylsiloxane is 10-40 Pa.s.
4. A high selectivity pervaporation gasoline desulfurization membrane, characterized in that it is produced by the production method of any one of claims 1 to 3, the permeation flux of said pervaporation gasoline desulfurization membrane being greater than or equal to 9.65Kg/m 2h, and the sulfur-rich factor being greater than or equal to 7.56.
5. The preparation method of the high-selectivity pervaporation gasoline desulfurization membrane comprises the following steps:
(1) Adding bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide into an absolute ethyl alcohol solvent to obtain an organosilicon solution A2 with the concentration of 0.2-0.6mol/L, dispersing a filler into a deionized water solvent to obtain a dispersion solution D with the concentration of 0.1-0.3mol/L, mixing and stirring the organosilicon solution A2 and the dispersion solution D uniformly according to the volume ratio of 1:1, reacting for 4-8 hours at the temperature of 35-45 ℃ under the catalysis of nitric acid, so that the bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide undergoes hydrolytic polymerization, and coating part of the organosilicon solution A2 on the surface of filler nano particles to obtain a sol solution B2; the filler is selected from one or more of CPO-27-Ni nano particles, cu < 2+ > -loaded UiO-67bpydc nano particles and MoS2 nano sheets;
(2) 10-20g of hydroxyl-terminated polydimethylsiloxane and 15-25g of polydimethylsiloxane are dissolved in 100g of organic solvent, and then 0.5g of organotin catalyst is added to obtain solution C;
(3) Mixing the sol solution B2 and the solution C according to the volume ratio of (3-8), and ultrasonically stirring to obtain uniform casting solution;
(4) Coating the casting solution on the surface of a ZrO2/Al2O3 support body after static defoaming, wherein the coating thickness is 15-35 mu m, drying in an oven at 110-120 ℃ for 8-12h, and crosslinking to form a film, so that a hydrolysis polymerization product of bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide, hydroxyl-terminated polydimethylsiloxane and polydimethylsiloxane are mutually crosslinked to form a film, and finally the pervaporation gasoline desulfurization film is obtained.
6. The method for preparing a high-selectivity pervaporation gasoline desulfurization membrane according to claim 5, wherein the organic solvent is one of hexane, heptane and octane; and/or the organotin catalyst is dibutyltin dilaurate; and/or the nitric acid is used in an amount of 1-3wt.% of the bis- (gamma-triethoxysilylpropyl) tetrasulfide or bis- (gamma-triethoxysilylpropyl) disulfide; and/or the ultrasonic stirring time is 15-45min.
7. The method for preparing a high selectivity pervaporation gasoline desulfurization membrane according to claim 6, wherein the viscosity of the hydroxyl-terminated polydimethylsiloxane is 1-5 Pa-s, and the viscosity of the polydimethylsiloxane is 10-40 Pa-s.
8. A high selectivity pervaporation gasoline desulfurization membrane, characterized in that it is produced by the production method of any one of claims 6 to 7, the permeation flux of which is greater than or equal to 12.15Kg/m 2h, and the sulfur-rich factor is greater than or equal to 8.33.
9. A high selectivity pervaporation gasoline desulfurization membrane according to claim 8, wherein the permeate flux of said membrane is 12.56Kg/m 2h and the sulfur-rich factor is 8.69.
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