CN100363094C - Preparation method of polyimide nanofiltration membrane - Google Patents
Preparation method of polyimide nanofiltration membrane Download PDFInfo
- Publication number
- CN100363094C CN100363094C CNB200510090148XA CN200510090148A CN100363094C CN 100363094 C CN100363094 C CN 100363094C CN B200510090148X A CNB200510090148X A CN B200510090148XA CN 200510090148 A CN200510090148 A CN 200510090148A CN 100363094 C CN100363094 C CN 100363094C
- Authority
- CN
- China
- Prior art keywords
- polyimide
- under
- film
- solution
- hours
- 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
- 229920001721 polyimide Polymers 0.000 title claims abstract description 89
- 239000004642 Polyimide Substances 0.000 title claims abstract description 67
- 239000012528 membrane Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001728 nano-filtration Methods 0.000 title abstract 8
- 239000010687 lubricating oil Substances 0.000 claims abstract description 42
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 238000005266 casting Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 238000001914 filtration Methods 0.000 claims description 38
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000003880 polar aprotic solvent Substances 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 13
- 230000001112 coagulating effect Effects 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 150000004984 aromatic diamines Chemical class 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 238000007872 degassing Methods 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 10
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isopropylhexane Natural products CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 claims description 10
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 8
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 7
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- -1 3,3 ' dimethyl diphenyl methane diamines Chemical class 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 abstract description 17
- 230000004907 flux Effects 0.000 abstract description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 13
- 150000002576 ketones Chemical class 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract 2
- 238000000614 phase inversion technique Methods 0.000 abstract 2
- 230000014759 maintenance of location Effects 0.000 abstract 1
- GQVCNZBQZKXBMX-UHFFFAOYSA-N butan-2-one;toluene Chemical compound CCC(C)=O.CC1=CC=CC=C1 GQVCNZBQZKXBMX-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000013459 approach Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000012805 post-processing Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002199 base oil Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001839 systemic circulation Effects 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of polyimide nanofiltration membrane for recovering lubricating oil ketone benzene dewaxing solvent, which comprises the steps of firstly preparing polyamic acid solution, adding additive to prepare polyamic acid nanofiltration membrane by phase inversion method, then carrying out chemical imidization on the membrane, carrying out solvent exchange and heat treatment to obtain the required polyimide nanofiltration membrane or preparing partially imidized polyimide which can be dissolved in some solvent, preparing the polyimide into membrane casting solution, forming the membrane by phase inversion method, and carrying out solvent and exchange and heat treatment to obtain the required nanofiltration membrane, wherein the preparation method can effectively reduce the preparation cost of the polyimide nanofiltration membrane, increase the polyimide variety which can be used for preparing the polyimide nanofiltration membrane, and increase the retention rate of the polyimide nanofiltration membrane on lubricating oil to be more than 90% at-18 ℃ to room temperature and under the operating pressure of 3MPa, the flux of the ketone-benzene mixed solvent is more than 12l/m2·h。
Description
Technical field
The present invention relates to a kind of preparation method who is used for the polyimide filtering membranes of lubricating oil benzol-kentone dewaxing solvent recovery.
Background technology
Known to those skilled in the art, for a long time, solvent dewaxing process in the production of lube base oil in the highest flight always.Solvent after the dewaxing (being methyl ethyl ketone and toluene) will be separated from the mixed liquor of lubricating oil and solvent with recycling by still-process, because the frequently freezing-heating-vaporization-condensation of solvent-cyclic process such as freezing grade, cause a large amount of consumption of energy, become the bottleneck that energy is expanded in lubricating oil and paraffin production.
Those of skill in the art attempt the method for separating by film for this reason process open up the new way of efficient a, low energy consumption.Application of membrane separation technology is in dewaxing technique, can be at low temperatures directly from the filtrate of dewaxed oil the cutting out partial cold solvent return systemic circulation and use, reduced the energy loss of high temperature distillation and cooling procedure, reduced the load of solvent recovery and refrigeration system simultaneously.Exxon-Mobil company was used for the solvent recovering system of dewaxing device with the diffusion barrier technology, had successfully realized industrialization in 1998.The diffusion barrier that this technology adopted is with commodity Matrimid by name
TMThe aromatic polyimide of 5218 complete imidizate is the NF membrane that membrane material makes by phase inversion.This kind Matrimid
TM5218 membrane materials are the soluble polyimide of complete imidizate, and price is extremely expensive.
Phase inversion is effective process means of preparation NF membrane, and many commodity NF membrane all are by this explained hereafter.Phase inversion prepares the NF membrane needs and polymeric film material and additive is dissolved in is mixed with casting solution in the solvent earlier, therefore requires polymeric film material to have solubility.Polyimides is to generate polyamic acid after imidizate makes by tetracarboxylic dianhydride and diamine polymerization.Because intermolecular cross-linking reaction takes place when imidizate easily for monomer structure, most of polyamic acids, the gained polyimides is insoluble material, is difficult to prepare required NF membrane by phase inversion.Owing to be subjected to the restriction of polyimide film material solubility property, the polyimide material of many function admirables, price cheapness can not utilize phase inversion to prepare polyimide filtering membranes like this.
In the process in the past, lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes is to utilize the soluble polyimide of complete imidizate to get by the phase inversion preparation.Do not have as yet at present earlier to make the polyamic acid NF membrane by phase inversion, then through obtain behind the chemical imidizate lubricating oil benzol-kentone dewaxing polyimide filtering membranes trial.Thereby do not have at present by adjusting chemical imidizate reagent dosage control degree of imidisation and then the deliquescent trial of control polyimide material yet, make it to utilize phase inversion to prepare polyimide filtering membranes.
Summary of the invention
The purpose of this invention is to provide and a kind ofly make the polyamic acid NF membrane by phase inversion, thereby then through obtaining lubricating oil benzol-kentone dewaxing polyimide filtering membranes behind the chemical imidizate or by adjusting the preparation method that chemical imidizate reagent dosage control degree of imidisation and then the preparation of control polyimide material dissolubility are used for the polyimide filtering membranes of lubricating oil benzol-kentone dewaxing solvent recovery.
The polyimide filtering membranes that is used for lubricating oil benzol-kentone dewaxing solvent recovery by two kinds of scheme preparations:
Scheme one:
Selected aromatic diamine is dissolved in the polar aprotic solvent, under nitrogen protection, in solution, add the aromatic series dianhydride, the addition of aromatic series dianhydride is the equal molar quantities of aromatic diamine, stirring reaction promptly obtained polyamic acid solution in 6～12 hours under the room temperature, the polar aprotic solvent consumption is that the polyimides acid concentration that will generate is controlled at 10～35wt% scope, and the best is the amount of 13～25wt%; With above-mentioned synthetic polyamic acid solution and water soluble polymer additives polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone, by polyamic acid: the weight ratio of water soluble polymer additive=100: 5～15 mixes, remove by filter insoluble impurities, filtrate is left standstill the degassing; Under 10～40 ℃, above-mentioned gained casting solution is coated at the bottom of the porous on the supporter, after 10～150 seconds volatilization time of control, immerse that freezing film obtains the polyamic acid NF membrane in the coagulating bath, coagulating bath is water or ethanol; The film rinsing after 24 hours, is deviate from 50% above moisture in vacuum drying oven, then film is immersed in by ethyl acetate: acetic anhydride: triethylamine is in the solution that mixes of 20: 2: 3 volume ratio, carries out chemical imidizate 10～16 hours under 30～50 ℃ of temperature; Film behind the imidizate respectively soaks 12 hours successively in isopropyl alcohol, hexane and glycerine after, under 100～150 ℃, handle obtaining lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 30～600 seconds.
Scheme two:
Aromatic diamine is dissolved in the polar aprotic solvent, under nitrogen protection, in solution, add the aromatic series dianhydride, the addition of aromatic series dianhydride is the equal molar quantities of aromatic diamine, stirring reaction promptly obtained polyamic acid solution in 6～12 hours under the room temperature, and the polar aprotic solvent consumption is the consumption that the polyimides acid concentration that will generate is controlled at 10～20wt% scope; Under agitation add chemical imidizate reagent and carry out chemical imidizate, chemistry imidizate reagent dosage is to add 100～800mL chemistry imidizate ratio of reagents by 1mol aromatic series dianhydride to add, the imidizate reagent solution that to be triethylamine and acetic anhydride mix by 3: 2 volume ratios, the imidizate time is 6 hours, solution after the imidization reaction is precipitated in water, obtain flaxen product, be drying to obtain the polyimide film material that dissolves in polar aprotic solvent after the washing; With gained polyimides, water soluble polymer additive and polar aprotic solvent by weight 0.25～0.35: 0.05～0.12: 1 proportional quantities places container, electromagnetic agitation makes it dissolving evenly under the room temperature, remove by filter insoluble impurities, filtrate is left standstill the degassing; Under 10～40 ℃, above-mentioned gained casting solution is coated at the bottom of the porous on the supporter, after 10～150 seconds volatilization time of control, immerse that freezing film obtains polyimide filtering membranes in water or the ethanol; After 24 hours, film respectively soaked in ethanol, isopropyl alcohol, hexane and glycerine 12 hours successively with the film rinsing, took out to handle under 100～150 ℃ to obtain lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 30～600 seconds.
Aromatic diamine is a diphenylmethane diamine (MDA), 4, and 4 '-diamines yl diphenyl ether (ODA) or 3,3 ' dimethyl diphenyl methane diamines (DMMDA) are the aromatic diamines with following structure:
The aromatic series dianhydride is pyromellitic acid dianhydride (PMDA), hexafluorodianhydride (6FDA) (6-FDA) or benzophenone tetracarboxylic dianhydride (BTDA), is the aromatic series dianhydride with following structure:
Polar aprotic solvent is N, N-dimethylacetylamide, N-methyl pyrrolidone, dimethyl formamide or methyl-sulfoxide.
The water soluble polymer additive is polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone.
Characteristics of the present invention are: the polyimide material of having avoided some kind is insoluble and be difficult to prepare the problem of benzol-kentone dewaxing with polyimide filtering membranes system film by phase inversion, thereby enlarged the kind of the polyimide material that can use, made it to select for use cheap polyimides to prepare polyimide filtering membranes.The polyamic acid NF membrane obtains the lubricating oil benzol-kentone dewaxing behind chemical acid imide can reduce the consumption of solvent and save polyimide film material precipitation, drying process when producing with the technological approaches of polyimide filtering membranes, reduced production cost.Therefore the benzol-kentone dewaxing of this preparation lubricating oil is simple with the preparation method of polyimide filtering membranes, can effectively reduce the manufacturing cost of polyimide filtering membranes.
The polyimide filtering membranes of preparing by above technical scheme can be used for being lubricated the recovery of oily benzol-kentone dewaxing solvent.Utilize Daqing petrochemical company industrial liquor (concentration of lubricating oil 18.3wt%, butanone-toluene by weight ratio are 1.2) to carry out the separating property evaluation of gained film.-18 ℃ to room temperature, under the operating pressure 3MPa, greater than 90%, the flux of ketone benzene mixed solvent is greater than 12L/m to the rejection of lubricating oil for the polyimide filtering membranes of preparing
2H.
The specific embodiment
Embodiment 1
Synthesizing of polyamic acid: with 4 of 5g (0.025mol); 4 '-diamines yl diphenyl ether (ODA) is dissolved in the N of 80_mL; in the N-dimethylacetylamide; electromagnetic agitation; the pyromellitic acid dianhydride (PMDA) that under nitrogen protection, in solution, in batches adds 5.45g (0.025mol); stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature, and the concentration of this solution is 13.1wt%.
The polyamic acid solution film-forming process: get above-mentioned synthetic polyamic acid solution 25g, add 2.0g polyvinylpyrrolidone additive, after mixing, filter with 300 order stainless (steel) wires, filtrate is left standstill the degassing 24 hours.Under dustless condition, under 25 ℃, relative humidity 50% situation, above-mentioned gained solution is coated on glass plate or the porous bottom, film forming thickness is controlled at about 25 μ m, the 25 seconds volatilization time of control, immerses film forming in the coagulating bath of water or ethanol then.
The post-processing approach of film: with film rinsing after 24 hours in coagulating bath, in vacuum drying oven, deviate from 50% above moisture, then film is immersed in by in ethyl acetate, acetic anhydride, the solution of triethylamine, under 30 ℃ of temperature, carried out chemical imidizate 12 hours by volume ratio mixing in 20: 2: 3.Film behind the imidizate respectively soaks 12 hours successively in isopropyl alcohol, hexane and glycerine after, under 120 ℃, handle obtaining lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 150 seconds.
Implementation result: the separating property of polyimide film is as follows: adopting the industrial liquor of Daqing petrochemical company is separate object, wherein concentration of lubricating oil 18.3wt%, butanone-toluene by weight ratio are 1.2, at room temperature, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 90.3% to the rejection of lubricating oil, and the flux of ketone benzene mixed solvent is 35.6L/m
2H.Under-18 ℃, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 93.2% to the rejection of lubricating oil, the flux of butanone-toluene mixed solvent is 18.6L/m
2H.
Embodiment 2
Synthesizing of polyamic acid: the diphenylmethane diamine (MDA) of 4.9568g (0.025mol) is dissolved in the N-methyl pyrrolidone of 80_mL; electromagnetic agitation; the benzophenone tetracarboxylic dianhydride (BTDA) that under nitrogen protection, in solution, in batches adds 8.0558g (0.025mol); stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature, and the concentration of this solution is 13.99wt%.
The polyamic acid solution film-forming process: get above-mentioned synthetic polyamic acid solution 25g, add 2.3g polyethylene glycol additive, after mixing, filter with 300 order stainless (steel) wires, filtrate is left standstill the degassing 24 hours.Under dustless condition, under 25 ℃, relative humidity 50% situation, above-mentioned gained solution is coated on glass plate or the porous bottom, film forming thickness is controlled at about 25 μ m, the 25 seconds volatilization time of control, immerses film forming in the coagulating bath of water or ethanol then.
The post-processing approach of film: with film rinsing after 24 hours in coagulating bath, in vacuum drying oven, deviate from 50% above moisture, then film is immersed in by in ethyl acetate, acetic anhydride, the solution of triethylamine, under 30 ℃ of temperature, carried out chemical imidizate 12 hours by volume ratio mixing in 20: 2: 3.Film behind the imidizate respectively soaks 12 hours successively in isopropyl alcohol, hexane and glycerine after, under 120 ℃, handle obtaining lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 150 seconds.
Implementation result: the separating property of polyimide film is as follows: adopting the industrial liquor of Daqing petrochemical company is separate object, wherein concentration of lubricating oil 18.3wt%, butanone-toluene by weight ratio are 1.2, at room temperature, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 96.3% to the rejection of lubricating oil, and the flux of ketone benzene mixed solvent is 28.4L/m
2H.Under-18 ℃, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 98.7% to the rejection of lubricating oil, the flux of butanone-toluene mixed solvent is 19.3L/m
2H.
Embodiment 3
Synthesizing of polyamic acid: with 3 of 5.658g (0.025mol); 3 ' dimethyl diphenyl methane diamines (DMMDA) is dissolved in the dimethyl formamide of 80_mL; electromagnetic agitation; the hexafluorodianhydride (6FDA) (6FDA) that under nitrogen protection, in solution, in batches adds 11.106g (0.025mol); stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature, and the concentration of this solution is 17.32wt%.
The polyamic acid solution film-forming process: get above-mentioned synthetic polyamic acid solution 25g, add 1.8g polyvinyl alcohol additive, after mixing, filter with 300 order stainless (steel) wires, filtrate is left standstill the degassing 24 hours.Under dustless condition, under 25 ℃, relative humidity 50% situation, above-mentioned gained solution is coated on glass plate or the porous bottom, film forming thickness is controlled at about 25 μ m, the 25 seconds volatilization time of control, immerses film forming in the coagulating bath of water or ethanol then.
The post-processing approach of film: with film rinsing after 24 hours in coagulating bath, in vacuum drying oven, deviate from 50% above moisture, then film is immersed in by in ethyl acetate, acetic anhydride, the solution of triethylamine, under 30 ℃ of temperature, carried out chemical imidizate 12 hours by volume ratio mixing in 20: 2: 3.Film behind the imidizate respectively soaks 12 hours successively in isopropyl alcohol, hexane and glycerine after, under 120 ℃, handle obtaining lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 150 seconds.
Implementation result: the separating property of polyimide film is as follows: adopting the industrial liquor of Daqing petrochemical company is separate object, wherein concentration of lubricating oil 18.3wt%, butanone-toluene by weight ratio are 1.2, at room temperature, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 95.8% to the rejection of lubricating oil, and the flux of butanone-toluene mixed solvent is 31.9L/m
2H.Under-18 ℃, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 97.2% to the rejection of lubricating oil, the flux of butanone-toluene mixed solvent is 16.5L/m
2H.
Embodiment 4
Synthesizing of soluble polyimide: the N that the diphenylmethane diamine (MDA) of 4.95g (0.025mol) is dissolved in 80mL; in the N-dimethylacetylamide; electromagnetic agitation; add the pyromellitic acid dianhydride (PMDA) of 5.45g (0.025mol) under nitrogen protection in solution, stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature in batches.Add the acetic anhydride of 6mL and the triethylamine of 9mL under stirring fast, stir under room temperature and finished the part imidizate in 6 hours, reaction solution precipitates in water, obtains flaxen product, after washing with water, is dried to constant weight under 50 ℃.
The preparation method of polyimide filtering membranes: get above-mentioned synthetic dried polyimides 10g, electromagnetic agitation makes it to be dissolved in 20mL N under the room temperature, in the mixed solvent of N-dimethylacetylamide and 16mL acetone, add 2.2g polyvinylpyrrolidone additive, dissolving evenly, after filtering with 300 order stainless (steel) wires, it is standby that filtrate is left standstill the degassing 24 hours.Under dustless, 25 ℃, relative humidity 50% condition, above-mentioned gained casting solution is coated on glass plate or the porous bottom, film forming thickness is controlled at about 25 μ m, the 30 seconds volatilization time of control, immerses film forming in the coagulating bath of water or ethanol then.
The post-processing approach of film: the film rinsing after 24 hours, was respectively soaked in ethanol, isopropyl alcohol, hexane and glycerine 12 hours successively, and taking-up is handled down at 100 ℃ and was obtained lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 300 seconds.
Implementation result: the separating property of polyimide film is as follows: adopting the industrial liquor of Daqing petrochemical company is separate object, wherein concentration of lubricating oil 18.3wt%, butanone-toluene by weight ratio are 1.2, at room temperature, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 97.8% to the rejection of lubricating oil, and the flux of butanone-toluene mixed solvent is 26.8L/m
2H.Under-18 ℃, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 98.5% to the rejection of lubricating oil, the flux of butanone-toluene mixed solvent is 13.5L/m
2H.
Embodiment 5
Synthesizing of soluble polyimide: with 3 of 5.658g (0.025mol); 3 ' dimethyl diphenyl methane diamines (DMMDA) is dissolved in the dimethyl formamide of 80_mL; electromagnetic agitation; the hexafluorodianhydride (6FDA) (6FDA) that under nitrogen protection, in solution, in batches adds 11.106g (0.025mol); stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature, and the concentration of this solution is 17.32wt%.Add the acetic anhydride of 6mL and the triethylamine of 9mL under stirring fast, stir under room temperature and finished the part imidizate in 6 hours, reaction solution precipitates in water, obtains flaxen product, after washing with water, is dried to constant weight under 50 ℃.
The preparation method of polyimide filtering membranes: get above-mentioned synthetic dried polyimides 10g, electromagnetic agitation makes it to be dissolved in 20mL N under the room temperature, in the mixed solvent of N-dimethylacetylamide and 16mL acetone, add 2.7g polyethylene glycol additive, dissolving evenly, after filtering with 300 order stainless (steel) wires, it is standby that filtrate is left standstill the degassing 24 hours.Under dustless, 25 ℃, relative humidity 50% condition, above-mentioned gained casting solution is coated on glass plate or the porous bottom, film forming thickness is controlled at about 25 μ m, the 30 seconds volatilization time of control, immerses film forming in the coagulating bath of water or ethanol then.
The post-processing approach of film: the film rinsing after 24 hours, was respectively soaked in ethanol, isopropyl alcohol, hexane and glycerine 12 hours successively, and taking-up is handled down at 100 ℃ and was obtained lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 300 seconds.
Implementation result: the separating property of polyimide film is as follows: adopting the industrial liquor of Daqing petrochemical company is separate object, wherein concentration of lubricating oil 18.3wt%, butanone-toluene by weight ratio are 1.2, at room temperature, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 96.4% to the rejection of lubricating oil, and the flux of butanone-toluene mixed solvent is 36.4L/m
2H.Under-18 ℃, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 98.9% to the rejection of lubricating oil, the flux of butanone-toluene mixed solvent is 17.8L/m
2H.
Embodiment 6
Synthesizing of soluble polyimide: with 4 of 5g (0.025mol); 4 '-diamines yl diphenyl ether (ODA) is dissolved in the methyl-sulfoxide of 80_mL; electromagnetic agitation; the benzophenone tetracarboxylic dianhydride (BTDA) that under nitrogen protection, in solution, in batches adds 8.0558g (0.025mol); stirring reaction promptly obtained polyamic acid solution in 8 hours under the room temperature, and the concentration of this solution is 14.03wt%.Add the acetic anhydride of 6mL and the triethylamine of 9mL under stirring fast, stir under room temperature and finished the part imidizate in 6 hours, reaction solution precipitates in water, obtains flaxen product, after washing with water, is dried to constant weight under 50 ℃.
The preparation method of polyimide filtering membranes: get above-mentioned synthetic dried polyimides 10g, electromagnetic agitation makes it to be dissolved in 20mL N under the room temperature, in the mixed solvent of N-dimethylacetylamide and 16mL acetone, add 1.6g polyvinyl alcohol additive, dissolving evenly, after filtering with 300 order stainless (steel) wires, it is standby that filtrate is left standstill the degassing 24 hours.Under dustless, 25 ℃, relative humidity 50% condition, above-mentioned gained casting solution is coated on glass plate or the porous bottom, film forming thickness is controlled at about 25 μ m, the 30 seconds volatilization time of control, immerses film forming in the coagulating bath of water or ethanol then.
The post-processing approach of film: the film rinsing after 24 hours, was respectively soaked in ethanol, isopropyl alcohol, hexane and glycerine 12 hours successively, and taking-up is handled down at 100 ℃ and was obtained lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 300 seconds.
Implementation result: the separating property of polyimide film is as follows: adopting the industrial liquor of Daqing petrochemical company is separate object, wherein concentration of lubricating oil 18.3wt%, butanone-toluene by weight ratio are 1.2, at room temperature, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 92.4% to the rejection of lubricating oil, and the flux of butanone-toluene mixed solvent is 38.7L/m
2H.Under-18 ℃, operating pressure 3MPa, when the feed liquid flow is 24L/h, prepared polyimide film is 93.6% to the rejection of lubricating oil, the flux of butanone-toluene mixed solvent is 18.1L/m
2H.
Claims (4)
1. the preparation method of a polyimide filtering membranes, it is characterized in that: aromatic diamine is dissolved in the polar aprotic solvent, under nitrogen protection, in solution, add the aromatic series dianhydride, the addition of aromatic series dianhydride is the equal molar quantities of aromatic diamine, stirring reaction promptly obtained polyamic acid solution in 6～12 hours under the room temperature, and the polar aprotic solvent consumption is that the polyimides acid concentration that will generate is controlled at 10～35wt% scope; With above-mentioned synthetic polyamic acid solution and water soluble polymer additives polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone, by polyamic acid: the weight ratio of water soluble polymer additive=100: 5～15 mixes, remove by filter insoluble impurities, filtrate is left standstill the degassing; Under 10～40 ℃, above-mentioned gained casting solution is coated at the bottom of the porous on the supporter, after 10～150 seconds volatilization time of control, immerse that freezing film obtains the polyamic acid NF membrane in the coagulating bath, coagulating bath is water or ethanol; The film rinsing after 24 hours, is deviate from 50% above moisture in vacuum drying oven, then film is immersed in by ethyl acetate: acetic anhydride: triethylamine is in the solution that mixes of 20: 2: 3 volume ratio, carries out chemical imidizate 10～16 hours under 30～50 ℃ of temperature; Film behind the imidizate respectively soaks 12 hours successively in isopropyl alcohol, hexane and glycerine after, under 100～150 ℃, handle obtaining lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 30～600 seconds;
Or aromatic diamine is dissolved in the polar aprotic solvent, under nitrogen protection, in solution, add the aromatic series dianhydride, the addition of aromatic series dianhydride is the equal molar quantities of aromatic diamine, stirring reaction promptly obtained polyamic acid solution in 6～12 hours under the room temperature, and the polar aprotic solvent consumption is the consumption that the polyimides acid concentration that will generate is controlled at 10～20wt% scope; Under agitation add chemical imidizate reagent and carry out chemical imidizate, chemistry imidizate reagent dosage is to add 100～800mL chemistry imidizate ratio of reagents by 1mol aromatic series dianhydride to add, the imidizate reagent solution that to be triethylamine and acetic anhydride mix by 3: 2 volume ratios, the imidizate time is 6 hours, solution after the imidization reaction is precipitated in water, obtain flaxen product, be drying to obtain the polyimide film material that dissolves in polar aprotic solvent after the washing; With gained polyimides, water soluble polymer additive and polar aprotic solvent by weight 0.25～0.35: 0.05～0.12: 1 proportional quantities places container, electromagnetic agitation makes it dissolving evenly under the room temperature, remove by filter insoluble impurities, filtrate is left standstill the degassing; Under 10～40 ℃, above-mentioned gained casting solution is coated at the bottom of the porous on the supporter, after 10～150 seconds volatilization time of control, immerse that freezing film obtains polyimide filtering membranes in water or the ethanol; After 24 hours, film respectively soaked in ethanol, isopropyl alcohol, hexane and glycerine 12 hours successively with the film rinsing, took out to handle under 100～150 ℃ to obtain lubricating oil benzol-kentone dewaxing solvent recovery polyimide filtering membranes in 30～600 seconds.
2. the preparation method of a kind of polyimide filtering membranes according to claim 1, it is characterized in that: aromatic diamine is a diphenylmethane diamine (MDA), 4,4 '-diamines yl diphenyl ether (ODA) or 3,3 ' dimethyl diphenyl methane diamines (DMMDA) is the aromatic diamine with following structure:
3. the preparation method of a kind of polyimide filtering membranes according to claim 1, it is characterized in that: the aromatic series dianhydride is pyromellitic acid dianhydride (PMDA), hexafluorodianhydride (6FDA) (6-FDA) or benzophenone tetracarboxylic dianhydride (BTDA), is the aromatic series dianhydride with following structure:
4. the preparation method of a kind of polyimide filtering membranes according to claim 1, it is characterized in that: polar aprotic solvent is N, N-dimethylacetylamide, N-methyl pyrrolidone, dimethyl formamide or methyl-sulfoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510090148XA CN100363094C (en) | 2005-08-11 | 2005-08-11 | Preparation method of polyimide nanofiltration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510090148XA CN100363094C (en) | 2005-08-11 | 2005-08-11 | Preparation method of polyimide nanofiltration membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1911494A CN1911494A (en) | 2007-02-14 |
| CN100363094C true CN100363094C (en) | 2008-01-23 |
Family
ID=37720647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510090148XA Active CN100363094C (en) | 2005-08-11 | 2005-08-11 | Preparation method of polyimide nanofiltration membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100363094C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106310961A (en) * | 2016-10-08 | 2017-01-11 | 天津科技大学 | Preparation method of lithium ion sieve acid-resistant blend membrane |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338217B (en) * | 2007-07-04 | 2012-03-07 | 中国石油天然气股份有限公司 | Method for manufacturing composite membrane for gasoline desulfurization |
| CN101420018B (en) * | 2007-10-26 | 2011-07-13 | 比亚迪股份有限公司 | Lithium ionic secondary cell barrier and preparation thereof |
| CN101992033A (en) * | 2009-08-28 | 2011-03-30 | 陈克 | Method for preparing polyimide hollow fiber pervaporation membrane and application thereof |
| CN101785977A (en) * | 2010-03-22 | 2010-07-28 | 北京化工大学 | Preparation method of solvent resistant polyimide nanofiltration film |
| CN103406030A (en) * | 2013-08-23 | 2013-11-27 | 哈尔滨工业大学 | Preparation method of gas-phase crosslinking modified polyetherimide nanofiltration membrane |
| JP7084683B2 (en) * | 2015-02-23 | 2022-06-15 | 東京応化工業株式会社 | Liquid purification method, chemical or cleaning liquid manufacturing method, filter media, and filter device |
| CN104817707B (en) * | 2015-04-05 | 2017-12-12 | 北京化工大学 | A kind of preparation method of high flux polyimide filtering membranes |
| CN105566907B (en) * | 2016-03-22 | 2018-11-06 | 天津工业大学 | A kind of polyimide filtering membranes and its method based on collaboration imidization preparation |
| CN106040011B (en) * | 2016-07-01 | 2018-09-14 | 哈尔滨工业大学宜兴环保研究院 | A kind of catechol and the end amido caged silsesquioxane method that coating prepares solvent resistant NF membrane altogether |
| CN107602857A (en) * | 2017-09-11 | 2018-01-19 | 中国石油大学(华东) | The preparation method and application of polyimides |
| CN109694746B (en) * | 2017-10-24 | 2021-11-19 | 中国石油化工股份有限公司 | Method for recovering dewaxing solvent for lube-oil feedstock and method for dewaxing lube-oil feedstock |
| CN109694724B (en) * | 2017-10-24 | 2022-03-15 | 中国石油化工股份有限公司 | Method for recovering dewaxing solvent for lube-oil feedstock and method for dewaxing lube-oil feedstock |
| CN109694744B (en) * | 2017-10-24 | 2022-03-15 | 中国石油化工股份有限公司 | Method for recovering dewaxing solvent for lube-oil feedstock and method for dewaxing lube-oil feedstock |
| CN109694745B (en) * | 2017-10-24 | 2021-09-21 | 中国石油化工股份有限公司 | Method for recovering dewaxing solvent for heavy lubricant oil feedstock and method for dewaxing heavy lubricant oil feedstock |
| CN109692572B (en) * | 2017-10-24 | 2022-03-29 | 中国石油化工股份有限公司 | Method for recovering dewaxing solvent for light lubricating oil raw oil and method for dewaxing light lubricating oil raw oil |
| CN108365151A (en) * | 2018-01-31 | 2018-08-03 | 青岛蓝科途膜材料有限公司 | A kind of polyimide high temperature-resistant lithium battery diaphragm and preparation method thereof |
| CN109745875A (en) * | 2019-03-05 | 2019-05-14 | 中复新水源科技有限公司 | A kind of preparation method of high throughput polyimides composite hyperfiltration membrane |
| CN114642971B (en) * | 2020-12-17 | 2023-01-20 | 沃顿科技股份有限公司 | Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same |
| CN113828165B (en) * | 2021-08-26 | 2022-07-15 | 哈尔滨工业大学（深圳） | Preparation method of polyvinyl alcohol ultrathin selective layer nanofiltration membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4347286A (en) * | 1980-02-25 | 1982-08-31 | Nitto Electric Industrial Co., Ltd. | Heat fusible polyimide compound films and process for producing the same |
| CN1313349A (en) * | 2000-02-22 | 2001-09-19 | 世韩工业株式会社 | Preparation of polyimide and polyamine acid |
-
2005
- 2005-08-11 CN CNB200510090148XA patent/CN100363094C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4347286A (en) * | 1980-02-25 | 1982-08-31 | Nitto Electric Industrial Co., Ltd. | Heat fusible polyimide compound films and process for producing the same |
| CN1313349A (en) * | 2000-02-22 | 2001-09-19 | 世韩工业株式会社 | Preparation of polyimide and polyamine acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106310961A (en) * | 2016-10-08 | 2017-01-11 | 天津科技大学 | Preparation method of lithium ion sieve acid-resistant blend membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1911494A (en) | 2007-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100363094C (en) | Preparation method of polyimide nanofiltration membrane | |
| CN108348871B (en) | Highly branched, non-crosslinked aerogels, method for the production thereof and use thereof | |
| CN108699277B (en) | Polymeric aerogels with improved mechanical and thermal properties | |
| US5074891A (en) | Method of gas separation and membranes therefor | |
| US5055116A (en) | Gas separation membranes comprising miscible blends of polyimide polymers | |
| CN105555838B (en) | For the self-crosslinkable of separation and the aromatic polyimide film through self-crosslinking | |
| US3822202A (en) | Heat treatment of membranes of selected polyimides,polyesters and polyamides | |
| CN106029742B (en) | With the highly selective polyimide film being made of block copolymerization acid imide for improving performance | |
| EP0087305B1 (en) | Process for production of aromatic polyimide film | |
| CN101837254B (en) | Method for preparing solvent-resistant polyimide nanofiltration membrane | |
| CN102946981A (en) | Polymers, polymer membranes and methods of producing the same | |
| CN109847585A (en) | The preparation method of composite nanometer filtering film and composite nanometer filtering film prepared therefrom | |
| Konagaya et al. | Synthesis of ternary copolyamides from aromatic diamine (m‐phenylenediamine, diaminodiphenylsulfone), aromatic diamine with carboxyl or sulfonic group (3, 5‐diaminobenzoic acid, 2, 4‐diaminobenzenesulfonic acid), and iso‐or terephthaloyl chloride | |
| CN105837819A (en) | Hybrid polyimide containing trifluoromethyl and oligomeric silsesquioxane structures at same time and preparation method thereof | |
| CN111019133A (en) | Polyimide resin for gas separation membrane, preparation method thereof and method for preparing polyimide gas separation membrane by using polyimide resin | |
| CN101785977A (en) | Preparation method of solvent resistant polyimide nanofiltration film | |
| CN109745875A (en) | A kind of preparation method of high throughput polyimides composite hyperfiltration membrane | |
| Zhou et al. | A thin-film composite polyarylester membrane prepared from orcinol and trimesoyl chloride for organic solvent nanofiltration | |
| CN110354684A (en) | A kind of reverse osmosis membrane of low energy consumption and its preparation method and application | |
| CN110527093A (en) | A kind of the sulfonation Cardo polyether sulfone polymer and synthetic method, reverse osmosis composite membrane of amino-contained | |
| EP0437611A1 (en) | Separative membrane made of aromatic polyimide | |
| CN109054017B (en) | Hyperbranched polyimide containing phenanthrene ring structure and preparation method and application thereof | |
| KR101477710B1 (en) | Novel polyimide derivatives, preparation method thereof and polymer gas separation membrane comprising the same | |
| CN113244788A (en) | Synthetic method and application of polyimide gas separation membrane material | |
| CN115260494B (en) | Polyimide and thin-layer composite film thereof and preparation method |
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 |