CN101327409B - Polyimides pervaporation membrane and preparation method and use - Google Patents
Polyimides pervaporation membrane and preparation method and use Download PDFInfo
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- CN101327409B CN101327409B CN2008100540396A CN200810054039A CN101327409B CN 101327409 B CN101327409 B CN 101327409B CN 2008100540396 A CN2008100540396 A CN 2008100540396A CN 200810054039 A CN200810054039 A CN 200810054039A CN 101327409 B CN101327409 B CN 101327409B
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Abstract
The present invention discloses a polyimide penetration vaporization film, and a method for preparing the polyimide penetration vaporization film and an application thereof. The polyimide penetration vaporization film is prepared with the following method: 4, 4'-diaminodiphenyl ether and 3,5-diaminobenzoic acid are solved in the solvent of N, N'-dimethyl acetamide, and benzene tetracarboxylic acid is added to have the polymerization reaction; the solution that is obtained after the polymerization reaction is kept statically for deaeration and then is knifed; under the room temperature, the solvent is volatilized to obtain the daiamid acid film; the daiamid acid film is immersed into the ethanol water solution to get a daiamid acid asymmetrical film; the daiamid acid asymmetrical film is immersed into the imidization agent that is composed of acetic anhydride, triethylamine and acetone, and then is taken out to get the polyimide penetration vaporization film. The polyimide penetration vaporization film of the present invention is used for penetrating, vaporizing and separating the normal-octane-thiofuran or the normal-heptane-thiofuran system.
Description
Technical field
The present invention relates to a kind of polyimides pervaporation membrane and Preparation method and use.
Background technology
Ten the most serious metropolitan primary pollution sources of global pollution all are vehicle exhausts at present, and producing clean fuel becomes the task of top priority.It is one of major pollutants of vehicle exhaust that the burning of gasoline and sulfide in diesel oil generates SOx, so various countries have formulated a series of new fuel oil sulfur-bearing standards, fuel oil low-sulfur and even do not have sulphur and become the inexorable trend that fuel oil cleans.On July 1st, 2005, China began to carry out Europe II vehicular emission standard, and the same year, Beijing began to carry out EUROIII Emission Standard, and the whole nation was pushed in expectation in 2010.In order to meet the Green Olympics, on March 1st, 2008, Beijing came into effect Europe IV discharge standard.During with enforcement Europe II vehicular emission standard oil quality is required to compare, require sulfur in gasoline content to drop to 150ppm by 500ppm when implementing Europe III vehicular emission standard, sulfur content drops to 350ppm by 500ppm in the diesel oil.Developed countries such as present America and Europe are limited in below the 30ppm the sulfur content in the gasoline, and the sulfur content in the diesel oil is limited in below the 50ppm.The sulfur content of domestic gasoline, diesel oil standard regulation is far longer than the setting in the American-European standard.China's oil product sulfur content is faced with the severe challenge of world's clean fuel standards.
Sulfide is a kind of novel desulfur technology in the film separation removal liquid fuel, and the pertinent literature report focuses mostly on greatly and adopts the infiltration evaporation membrane separation technique.The infiltration evaporation membrane separation technique is under the promotion of component steam pressure difference in liquid mixture, utilize component by the dissolving of film and the different separating process that realize of diffusion rate, be mainly used in organics dehydration, underwater micro-organic matter and remove, closely boil or constant boiling mixture separates, forms the separation of extremely asymmetric system etc.Infiltration evaporation has tangible technical advantage, outstanding characteristics be selectivity height, good stability, low energy consumption, environmental friendliness, simple to operate, be easy to amplify.The work of infiltrating and vaporizing membrane Research of Separation Technique concentrates on finds that high score is from performance and stable membrane material.
The desulfurizing oil system belongs to the organic liquor mixture, requires infiltrating and vaporizing membrane to have solvent resistance and higher mechanical strength.At present, the infiltrating and vaporizing membrane that the more oil product sulphur of domestic and international research is used mainly is the membrane material of preferential saturating sulphur, as nonionic film (film that polyvinylpyrrolidone and Triafol T etc. are made), ionic membrane (Nafion RTM type film), pvf film, polyethylene glycol film, polysiloxane film etc.
Polyimide material has caused many researchers' very big interest as the anti-solvent of a class, chemicals-resistant, high temperature resistant, high performance membrane material that mechanical performance is excellent.Polyimide film is showing higher selection permeability aspect the gas separation, therefore be widely used in gas and separate.The monomer for preparing polyimides in addition has diversity, can therefore help studying the dissolving diffusion mechanism of infiltration evaporation by changing structure and the character that polymerization single polymerization monomer changes polyimide film, improves the separating property of polyimide film.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of polyimides pervaporation membrane is provided.
Second purpose of the present invention provides a kind of preparation method of polyimides pervaporation membrane.
The 3rd purpose of the present invention provides a kind of purposes of polyimides pervaporation membrane.
Technical scheme of the present invention is summarized as follows:
Polyimides pervaporation membrane, make with following method:
(1) with 4,4 '-diaminodiphenyl ether (ODA) and 3,5-diaminobenzoic acid (DABA) is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.35～0.50mol/L, make 3, the molar concentration of 5-diaminobenzoic acid is 0～0.09mol/L; Add pyromellitic dianhydride (PMDA) and carry out polymerisation 3～7h at 0 ℃～40 ℃, described pyromellitic dianhydride and described 4,4 '-mol ratio of diaminodiphenyl ether is 1: 1～1.3: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 1～5h, make polyamide acid film, it is to soak 5～20min in 5%～40% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) described polyamic acid asymmetric membrane being immersed in volume ratio is 2～5: 1～4: 24h～48h in the imidization agent that 10～20 acetic anhydride, triethylamine and acetone are formed, take out, and promptly obtain polyimides pervaporation membrane.
In the step (1) 4,4 '-the preferred 0.40mol/L～0.45mol/L of molar concentration of diaminodiphenyl ether.
In the step (1) 3, the preferred 0.02mol/L～0.03mol/L of the molar concentration of 5-diaminobenzoic acid.
Preferred 4: 2: 15 of the volume ratio of the middle acetic anhydride of step (3), triethylamine and acetone.
The preparation method of polyimides pervaporation membrane, be made up of following step:
(1) with 4,4 '-diaminodiphenyl ether and 3, the 5-diaminobenzoic acid is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.35～0.50mol/L, make 3, the molar concentration of 5-diaminobenzoic acid is 0～0.09mol/L; Add pyromellitic dianhydride and carry out polymerisation 3～7h at 0 ℃～40 ℃, described pyromellitic dianhydride and described 4,4 '-mol ratio of diaminodiphenyl ether is 1: 1～1.3: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 1～5h, make polyamide acid film, it is to soak 5～20min in 5%～40% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) described polyamic acid asymmetric membrane being immersed in volume ratio is 2～5: 1～4: 24h～48h in the imidization agent that 10～20 acetic anhydride, triethylamine and acetone are formed, take out, and promptly obtain polyimides pervaporation membrane.
In the step (1) 4,4 '-the preferred 0.40mol/L～0.45mol/L of molar concentration of diaminodiphenyl ether.
In the step (1) 3, the preferred 0.02mol/L～0.03mol/L of the molar concentration of 5-diaminobenzoic acid.
Preferred 4: 2: 15 of the volume ratio of the middle acetic anhydride of step (3), triethylamine and acetone.
The purposes of polyimides pervaporation membrane is used to separate normal octane-thiophene or normal heptane-thiophene.
The quality swelling coefficient of polyimides pervaporation membrane of the present invention in 50 ℃ of material liquids is lower than 0.15kg/kg, be used for infiltration evaporation and separate normal octane-thiophene or normal heptane-thiophene system, the initial content of thiophene is 1000～100 μ g/g in the material liquid, the material liquid temperature is 30～60 ℃, film chamber per-meate side vacuum is 50～100kPa, and obtainable permeation flux is 0.20～3.5kg/m
2H is 0.5～6 to the separation factor of thiophene.If the adding volume fraction is 1%～10% ethanol in the initial feed, can effectively improve the selection permeability of polyimides pervaporation membrane to thiophene, make film high 2～10 times than normal octane to the penetrated preferably of thiophene.
Description of drawings
Fig. 1 is the infrared spectrogram of polyimides pervaporation membrane of the present invention;
Fig. 2 is flux and the separation factor that polyimides pervaporation membrane of the present invention separates thiophene-octane mixture;
Fig. 3 is flux and the separation factor that polyimides pervaporation membrane of the present invention separates thiophene-octane-alcohol mixture.
The specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Polyimides pervaporation membrane, make with following method:
(1) with 4,4 '-diaminodiphenyl ether and 3, the mixing of 5-diaminobenzoic acid is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.40mol/L, make 3, the molar concentration of 5-diaminobenzoic acid is 0.02mol/L, adds pyromellitic dianhydride, at 30 ℃ at N
2Carry out polymerisation 5h under the protection, described pyromellitic dianhydride and described 4,4 '-mol ratio of diaminodiphenyl ether is 1: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 3h, make polyamide acid film, it is to soak 10min in 35% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) described polyamic acid asymmetric membrane being immersed in volume ratio is 48h in the imidization agent formed of 3: 1: 12 acetic anhydride, triethylamine and acetone, takes out, and promptly obtains polyimides pervaporation membrane.
The infrared spectrogram of polyimides pervaporation membrane is seen Fig. 1.
1720cm among Fig. 1
-1And 1780cm
-1The absworption peak at place is respectively C=O symmetrical stretching vibration absworption peak and asymmetric stretching vibration absworption peak in the imide bond, 1380cm
-1The absworption peak at place is a C-N stretching vibration absworption peak in the imide bond, 729cm
-1The absworption peak at place is a C=O flexural vibrations absworption peak in the imide bond.The polyimides pervaporation membrane of PMDA-ODA/5%DABA is at 3600-2500cm
-1Very wide O-H characteristic absorption peak has appearred in the zone.
Polyimides pervaporation membrane, make with following method:
(1) with 4,4 '-diaminodiphenyl ether and 3, the 5-diaminobenzoic acid is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.40mol/L, makes 3, the molar concentration of 5-diaminobenzoic acid is 0.02mol/L; Add pyromellitic dianhydride and carry out polymerisation 3h at 40 ℃, pyromellitic dianhydride and 4,4 '-mol ratio of diaminodiphenyl ether is 1: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 1h, make polyamide acid film, it is to soak 15min in 20% the ethanol water that polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) the polyamic acid asymmetric membrane being immersed in volume ratio is 30h in the imidization agent formed of 2: 4: 15 acetic anhydride, triethylamine and acetone, takes out, and promptly obtains polyimides pervaporation membrane.
Polyimides pervaporation membrane, make with following method:
(1) with 4,4 '-diaminodiphenyl ether and 3, the 5-diaminobenzoic acid is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.45mol/L, makes 3, the molar concentration of 5-diaminobenzoic acid is 0.03mol/L; Add pyromellitic dianhydride and carry out polymerisation 7h at 0 ℃, pyromellitic dianhydride and 4,4 '-mol ratio of diaminodiphenyl ether is 1.3: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 5h, make polyamide acid film, it is to soak 10min in 30% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) the polyamic acid asymmetric membrane being immersed in volume ratio is 48h in the imidization agent formed of 3: 1: 12 acetic anhydride, triethylamine and acetone, takes out, and promptly obtains polyimides pervaporation membrane.
Polyimides pervaporation membrane is to make with following method:
(1) with 4,4 '-diaminodiphenyl ether and 3, the 5-diaminobenzoic acid is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.35mol/L, makes 3, the molar concentration of 5-diaminobenzoic acid is 0.09mol/L; Add pyromellitic dianhydride and carry out polymerisation 5h at 10 ℃, pyromellitic dianhydride and 4,4 '-mol ratio of diaminodiphenyl ether is 1.2: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 4h, make polyamide acid film, it is to soak 20min in 5% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) the polyamic acid asymmetric membrane being immersed in volume ratio is 24h in the imidization agent formed of 5: 3: 10 acetic anhydride, triethylamine and acetone, takes out, and promptly obtains polyimides pervaporation membrane.
Polyimides pervaporation membrane, make with following method:
(1) with 4,4 '-diaminodiphenyl ether is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.50mol/L; Add pyromellitic dianhydride and carry out polymerisation 4h at 20 ℃, pyromellitic dianhydride and 4,4 '-mol ratio of diaminodiphenyl ether is 1.2: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 3h, make polyamide acid film, it is to soak 5～20min in 40% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) the polyamic acid asymmetric membrane being immersed in volume ratio is 36h in the imidization agent formed of 4: 2: 20 acetic anhydride, triethylamine and acetone, takes out, and promptly obtains polyimides pervaporation membrane.
The polyimides pervaporation membrane infiltration evaporation of present embodiment preparation separates the normal octane/thiophene system that contains thiophene 800ppm, and 50 ℃ of film room temperatures, per-meate side vacuum are 80kPa, and the acquisition permeation flux is 1.3kg/m
2H, the selective permeation thiophene, separation factor can reach 3.2.The polyimides pervaporation membrane that present embodiment is made carries out infiltration evaporation and separates the permeation flux of normal octane/thiophene mixture and separation factor with the variation relation of operating time as shown in Figure 2.
Made polyimide film infiltration evaporation separates and contains ethanol 2%, contains normal octane/thiophene system of thiophene 800ppm, and 50 ℃ of film room temperatures, per-meate side vacuum are 80kPa, and can obtain permeation flux is 2.0kg/m
2H compares with normal octane, and the separation factor of selective permeation thiophene is increased to 6.2.The polyimides pervaporation membrane that present embodiment is made carries out infiltration evaporation and separates the permeation flux of normal octane-thiophene-alcohol mixture and separation factor with the variation relation of operating time as shown in Figure 3.
Polyimides pervaporation membrane, make with following method:
(1) with 4,4 '-diaminodiphenyl ether and 3, the 5-diaminobenzoic acid is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.45mol/L, makes 3, the molar concentration of 5-diaminobenzoic acid is 0.03mol/L; Add pyromellitic dianhydride and carry out polymerisation 7h at 0 ℃, described pyromellitic dianhydride and described 4,4 '-mol ratio of diaminodiphenyl ether is 1: 2: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 3h, make polyamide acid film, it is to soak 15min in 30% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) described polyamic acid asymmetric membrane being immersed in volume ratio is 30h in the imidization agent formed of 4: 2: 15 acetic anhydride, triethylamine and acetone, takes out, and promptly obtains polyimides pervaporation membrane.
Polyimides pervaporation membrane, make with following method:
(1) with 4,4 '-diaminodiphenyl ether and 3, the 5-diaminobenzoic acid is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.45mol/L, makes 3, the molar concentration of 5-diaminobenzoic acid is 0.03mol/L; Add pyromellitic dianhydride and carry out polymerisation 7h at 0 ℃, described pyromellitic dianhydride and described 4,4 '-mol ratio of diaminodiphenyl ether is 1: 2: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 3h, make polyamide acid film, it is to soak 15min in 30% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) described polyamic acid asymmetric membrane being immersed in volume ratio is 30h in the imidization agent formed of 5: 2: 20 acetic anhydride, triethylamine and acetone, takes out, and promptly obtains polyimides pervaporation membrane.
The made polyimides pervaporation membrane of the present invention is used for infiltration evaporation and separates normal octane-thiophene or normal heptane-thiophene system, thiophene quality percentage composition is 2000～100ppm in the initial feed, the film room temperature is 30～60 ℃, it is 50～100kPa that vacuum is surveyed in the infiltration of film chamber, and can obtain the film permeation flux is 0.20～3.5kg/m
2H is 0.5～5 to the separation factor of thiophene.If the adding volume fraction is 1%～10% ethanol in the initial feed, can effectively improve the selection permeability of polyimide film to thiophene, the separation factor that makes film select permeability to see through thiophene improves 2～10 times than normal octane, normal heptane.
Claims (9)
1. polyimides pervaporation membrane is characterized in that making with following method:
(1) with 4,4 '-diaminodiphenyl ether and 3, the 5-diaminobenzoic acid is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.35～0.50mol/L, make 3, the molar concentration of 5-diaminobenzoic acid is 0～0.09mol/L; Add pyromellitic dianhydride and carry out polymerisation 3～7h at 0 ℃～40 ℃, described pyromellitic dianhydride and described 4,4 '-mol ratio of diaminodiphenyl ether is 1: 1～1.3: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 1～5h, make polyamide acid film, it is to soak 5～20min in 5%～40% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) described polyamic acid asymmetric membrane being immersed in volume ratio is 2～5: 1～4: 24h～48h in the imidization agent that 10～20 acetic anhydride, triethylamine and acetone are formed, take out, and promptly obtain polyimides pervaporation membrane.
2. a kind of polyimides pervaporation membrane according to claim 1, it is characterized in that described in the described step (1) 4,4 '-molar concentration of diaminodiphenyl ether is 0.40mol/L～0.45mol/L.
3. a kind of polyimides pervaporation membrane according to claim 1 is characterized in that described in the described step (1) 3, and the molar concentration of 5-diaminobenzoic acid is 0.02mol/L～0.03mol/L.
4. a kind of polyimides pervaporation membrane according to claim 1, the volume ratio that it is characterized in that acetic anhydride, triethylamine and acetone described in the described step (3) is 4: 2: 15.
5. the preparation method of polyimides pervaporation membrane, its feature is made up of following step:
(1) with 4,4 '-diaminodiphenyl ether and 3, the 5-diaminobenzoic acid is dissolved in solvent N, in N '-dimethylacetylamide, make 4,4 '-molar concentration of diaminodiphenyl ether is 0.35～0.50mol/L, make 3, the molar concentration of 5-diaminobenzoic acid is 0～0.09mol/L; Add pyromellitic dianhydride and carry out polymerisation 3～7h at 0 ℃～40 ℃, described pyromellitic dianhydride and described 4,4 '-mol ratio of diaminodiphenyl ether is 1: 1～1.3: 1; With knifing after the solution left standstill deaeration that obtains after the polymerisation, at room temperature make solvent evaporates 1～5h, make polyamide acid film, it is to soak 5～20min in 5%～40% the ethanol water that described polyamide acid film is immersed concentration expressed in percentage by volume, promptly obtains the polyamic acid asymmetric membrane;
(2) described polyamic acid asymmetric membrane being immersed in volume ratio is 2～5: 1～4: 24h～48h in the imidization agent that 10～20 acetic anhydride, triethylamine and acetone are formed, take out, and promptly obtain polyimides pervaporation membrane.
6. the preparation method of a kind of polyimides pervaporation membrane according to claim 5, it is characterized in that described in the described step (1) 4,4 '-molar concentration of diaminodiphenyl ether is 0.40mol/L～0.45mol/L.
7. the preparation method of a kind of polyimides pervaporation membrane according to claim 5 is characterized in that described in the described step (1) 3, and the molar concentration of 5-diaminobenzoic acid is 0.02mol/L～0.03mol/L.
8. the preparation method of a kind of polyimides pervaporation membrane according to claim 5, the volume ratio that it is characterized in that acetic anhydride, triethylamine and acetone described in the described step (2) is 4: 2: 15.
9. the purposes of the polyimides pervaporation membrane of one of claim 1～4 is characterized in that being used to separate normal octane-thiophene or normal heptane-thiophene.
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| CN106310961A (en) * | 2016-10-08 | 2017-01-11 | 天津科技大学 | Preparation method of lithium ion sieve acid-resistant blend membrane |
| CN109126469B (en) * | 2018-09-01 | 2021-05-04 | 常州大学 | Preparation method and application of polyimide/inorganic particle pervaporation hybrid membrane |
| CN112705050B (en) * | 2019-10-24 | 2022-12-09 | 中国石油化工股份有限公司 | Polyimide pervaporation separation membrane and preparation method and separation method thereof |
| CN111302324B (en) * | 2020-02-20 | 2021-10-22 | 西安工程大学 | Magnetic microporous carbon-based wave-absorbing composite material and preparation method thereof |
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