CN104128102B - A kind of cyclo-dextrin-modified compounded organic solvent NF membrane and preparation method thereof - Google Patents
A kind of cyclo-dextrin-modified compounded organic solvent NF membrane and preparation method thereof Download PDFInfo
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- CN104128102B CN104128102B CN201410378550.7A CN201410378550A CN104128102B CN 104128102 B CN104128102 B CN 104128102B CN 201410378550 A CN201410378550 A CN 201410378550A CN 104128102 B CN104128102 B CN 104128102B
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Abstract
The invention discloses a kind of cyclo-dextrin-modified compounded organic solvent NF membrane and preparation method thereof, belong to technical field of membrane.Its key technology is: with hydrolyzed modified polyacrylonitrile ultrafiltration film for basement membrane, prepare aqueous phase solution with aminated compounds and cyclodextrin and cast on basement membrane, then cast with the organic phase solution containing acyl chloride compound, prepare compound (separation) layer by interface polymerization reaction; Cyclo-dextrin-modified compounded organic solvent NF membrane is obtained finally by vacuum drying.This NF membrane has good solvent resistant characteristic and heat endurance in alcohols, ester class, ketone, alkanes and benzene class organic solvent; To alcohols, ester class, ketone, alkanes and benzene class organic solvent, there is certain selective penetrated property; Change preparation condition, can the permeation flux of controlling diaphragm and cutoff performance, to adapt to the requirement of practical application.This film is particularly suitable for the nanofiltration of alcohols and alkanes organic solvent.
Description
Technical field
The invention belongs to technical field of membrane, particularly a kind of cyclo-dextrin-modified compounded organic solvent NF membrane and preparation method thereof.
Background technology
Organic solvent nanofiltration (SRNF) is promising clean, the high efficient separation technology of a kind of tool, be widely used in the separation of organic solvent system, as in pharmaceutical industry polypeptide drugs preparation process, nanofiltration process can improve whole polypeptide down stream train, solves a large-scale production difficult problem for restriction polypeptide industrial development; In mineral oil separation process, for heavy constituent removal in the separation of free fatty vegetable oil and coalification oil refining, the application of organic solvent nanofiltration technology is capable of reducing energy consumption, simplification solvent handling process.Organic solvent nanofiltration film is the core component of organic solvent nanofiltration (SRNF), and commercial solvent resistant NF membrane mainly contains silicone rubber membrane and polyimide film.Silicone rubber membrane has the large advantage of flux in non-polar solven, but it excessively swellingly makes its poor selectivity, and to polar solvent, then flux is very little; Polyimide film can resistance to polarity, aprotic solvent, but does not substantially have flux for non-polar solven, is not suitable for for alkane solvent.In organic solvent nanofiltration field, commercially produced product is foreign brand name, and domestic solvent resistant NF membrane work is ground zero, is mostly in development.
Based on the chemical characteristic that organic solvent kind is a lot, the development of organic solvent nanofiltration film need solve two problems: (1) solvent resistance: organic solvent nanofiltration film keeps good chemical stability in organic solvent; (2) excellent stalling characteristic: organic solvent nanofiltration film has good selective and higher flux in organic solvent.In order to realize this target, researcher has carried out a large amount of work, as (1) carries out hydrophilic/hydrophobic modification with to existing film, comprises gas ions process, ozone-ultraviolet radiation, surfactant process and graft copolymerization process etc.; (2) develop specific organic solvent and transmit material, comprise zeolite, molecular sieve, organo-metallic compound etc.
Cyclodextrin (CD) is a kind of typical both sexes annular molecule, and its outer wall is rich in the two-dimensional structure of hydrophilic radical (hydroxy), and its polymolecularity makes CD become a kind of well polymer compound film packing material; Its inwall presents hydrophobicity and suitable with organic solvent molecule diameter due to cage effect, and is insoluble to common organic solvents, can be used as organic solvent molecule transmission channels.Not yet there is the research report utilizing cyclodextrin to strengthen organic solvent nanofiltration UF membrane characteristic aspect at present.
Summary of the invention
The object of this invention is to provide a kind of solvent resistant, cyclo-dextrin-modified compounded organic solvent NF membrane that separating property is good; Another object is to provide its preparation method.
For realizing the object of the invention, cyclodextrin is introduced NF membrane separating layer and is prepared a kind of cyclo-dextrin-modified compounded organic solvent NF membrane by the present invention.The present invention is subject to plant leaf blade pore and inspires, and utilizes the hydrophilic radical of cyclodextrin outer wall to make to obtain good compatibility between itself and polymer; Nonpolar molecule is to the dissolving of cyclodextrin inner chamber to utilize its inwall relative hydrophobic characteristic to promote, thus significantly enhances non-polar solven transmission characteristic.The technical solution used in the present invention is: take polyacrylonitrile ultrafiltration film as basement membrane, prepare aqueous phase solution with aminated compounds and cyclodextrin and cast on basement membrane, then cast with the organic phase solution containing acyl chloride compound, prepare compound (separation) layer by interface polymerization reaction; Organic solvent nanofiltration film is obtained finally by vacuum drying.Described polyacrylonitrile ultrafiltration film molecular cut off is 10,000 ~ 200,000;
Described aminated compounds is the one of polymine, m-phenylene diamine (MPD), piperazine and polyepichlorohydrin amine, or the mixture of two kinds of compounds;
Described acyl chloride compound refers to the one of pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, or the mixture of two kinds of compounds;
Described cyclodextrin has three types, comprises α cyclodextrin, beta cyclodextrin, γ cyclodextrin.
Concrete masking step is as follows:
(1) polyacrylonitrile ultrafiltration film being immersed into concentration is 0.3 ~ 2.5mol ﹒ L
-1sodium hydrate aqueous solution in, submergence reaction at 30 ~ 80 DEG C, take out subsequently and in deionized water fully washing obtain the polyacrylonitrile ultrafiltration film that is hydrolyzed;
(2) add in deionized water by cyclodextrin, at room temperature ultrasonic process is to being uniformly dispersed; Again aminated compounds is joined in above-mentioned cyclodextrin aqueous solution, continue to be stirred to and evenly obtain aqueous phase solution.Wherein aminated compounds addition is 1% ~ 5% of solution weight; Cyclodextrin addition is 0.01% ~ 0.2% of solution weight;
(3) cast on the polyacrylonitrile ultrafiltration film after hydrolysis process by aqueous phase solution, remove aqueous phase solution after soaking at room temperature, drying at room temperature makes face remove moisture;
(4) acyl chloride compound is dissolved in hexane solution and obtains organic phase solution, wherein acyl chloride compound addition is 1% ~ 5% of solution weight;
(5) organic phase solution is cast on the basement membrane of step (3) gained, react under room temperature, after reaction terminates, remove organic phase solution.Acyl chloride compound and aminated compounds and cyclodextrin react and form compound (separation) layer.
(6) basement membrane being compounded with interfacial polymerization layer is taken out, be placed in vacuum constant temperature drying box and heat-treat, obtain compounded organic solvent NF membrane.Heat treatment temperature preferably 50 ~ 90 DEG C, heat treatment time preferably 10 ~ 80 minutes.
Obtained cyclo-dextrin-modified compounded organic solvent NF membrane separating layer thickness is 250-400nm.
The innovative point of above-mentioned process route is: polyacrylonitrile ultrafiltration film is hydrolyzed by (1), and can produce carboxyl after polyacrylonitrile ultrafiltration film hydrolysis, the amido in the aminated compounds of this carboxyl and coating reacts, and makes interfacial polymerization layer and support pass through chemical bonds; (2) acyl chloride compound and aminated compounds and cyclodextrin react and form compound (separation) layer; (3) cyclodextrin add drastically increase alkanes solvent through ability.(4) change the type of cyclodextrin, the organic solvent film that performance is different can be obtained; Different according to adding cyclodextrin kind, be designated as alpha-cyclodextrin film respectively, beta-schardinger dextrin-film and gamma-cyclodextrin film.
The cyclo-dextrin-modified compounded organic solvent NF membrane that the present invention obtains is area swellbility≤5% in alcohols, ester class, ketone, alkanes and benzene class organic solvent, shows that film has good solvent resistant characteristic; Thermogravimetric analysis (TGA) shows initial degradation temperature >=320 DEG C of film, shows that film has good heat endurance; Film has certain selective penetrated property to alcohols, ester class, ketone, alkanes and benzene class organic solvent; Wherein alpha-cyclodextrin film to the rejection of PEG400 all higher than 90%; Beta-schardinger dextrin-film to the rejection of PEG600 all higher than 90%; Gamma-cyclodextrin film to the rejection of PEG4000 all higher than 90%.The flux of cyclo-dextrin-modified compounded organic solvent NF membrane to isopropyl alcohol and normal heptane is comparatively large, and the flux of ethyl acetate, butanone is placed in the middle; Toluene flux is less.Cyclo-dextrin-modified compounded organic solvent NF membrane of the present invention is particularly suitable for the nanofiltration of alcohols and alkanes organic solvent.
Accompanying drawing explanation
The structural formula of Fig. 1 cyclodextrin;
Fig. 2 polyacrylonitrile ultrafiltration film surface scan electromicroscopic photograph;
The beta-schardinger dextrin-film surface scan electromicroscopic photograph that Fig. 3 the present invention obtains;
The beta-schardinger dextrin-film profile scanning electromicroscopic photograph that Fig. 4 the present invention obtains.
Detailed description of the invention
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
The polyacrylonitrile ultrafiltration film of molecular cut off 10,000 is immersed into 2.0mol ﹒ L
-1in sodium hydrate aqueous solution, submergence 1h under 50 DEG C of conditions, takes out subsequently and fully washs by deionized water the polyacrylonitrile ultrafiltration film obtaining hydrolysis process at ambient temperature.
α cyclodextrin is joined in deionized water, at room temperature ultrasonic process 1h; Joined by piperazine in above-mentioned cyclodextrin aqueous solution, continue ultrasonic agitation 1h and obtain aqueous phase solution, wherein piperazine addition is 3%, α cyclodextrin addition of solution weight is 0.03% of solution weight again.Cast on the polyacrylonitrile ultrafiltration film of hydrolysis process by the aqueous phase solution of gained, remove film excess surface solution after soaking at room temperature 20min, drying at room temperature makes face remove moisture; Cast on the polyacrylonitrile ultrafiltration film of above-mentioned gained with the hexane solution of the pyromellitic trimethylsilyl chloride of mass percent 3% subsequently, normal temperature crosslinked 8min, removes organic phase solution; Dry 60min at 60 DEG C again, obtains cyclo-dextrin-modified rice compounded organic solvent NF membrane.Gained film is designated as α cyclodextrin film.
α cyclodextrin film area swellbility in isopropyl alcohol, ethyl acetate, butanone, normal heptane and toluene is less than 4.3%, and thermogravimetric analysis (TGA) shows that the initial degradation temperature of film is 324.1 DEG C, and namely film has good heat endurance.Under room temperature and 1MPa condition, α cyclodextrin film to the rejection of PEG400 all higher than 90%; The flux of α cyclodextrin film to isopropyl alcohol, ethyl acetate, butanone and normal heptane is respectively 25.3,14.2,13.4 and 21.2L ﹒ m
-2﹒ h
-1, toluene flux is 6.50L ﹒ m
-2﹒ h
-1.
Embodiment 2
The polyacrylonitrile ultrafiltration film of molecular cut off 100,000 is immersed into 1.0mol ﹒ L
-1in sodium hydrate aqueous solution, submergence 1h under 50 DEG C of conditions, takes out subsequently and fully washs by deionized water the polyacrylonitrile ultrafiltration film obtaining hydrolysis process at ambient temperature.
Beta cyclodextrin is joined in deionized water, at room temperature ultrasonic process 2h; Again polymine is joined in above-mentioned cyclodextrin aqueous solution, continue ultrasonic agitation 1h and obtain aqueous phase solution, Qi Zhongshui: polymine: beta cyclodextrin=25:1:0.03(mass ratio).Cast on the polyacrylonitrile ultrafiltration film of hydrolysis process by the casting solution of gained, remove film excess surface solution after soaking at room temperature 10min, drying at room temperature makes face remove moisture; Cast on the polyacrylonitrile ultrafiltration film of above-mentioned gained with the hexane solution of the pyromellitic trimethylsilyl chloride of mass percent 4% subsequently, normal temperature crosslinked 12min, removes organic phase solution; Dry 60min at 60 DEG C again, obtains nano combined organic solvent nanofiltration film.Gained film is designated as beta cyclodextrin film.
Beta cyclodextrin film area swellbility in isopropyl alcohol, ethyl acetate, butanone, normal heptane and toluene is less than 4.5%, and it is 326.3 DEG C that thermogravimetric analysis (TGA) records its initial degradation temperature, and namely film has good heat endurance.Under room temperature and 1MPa condition, beta cyclodextrin film to the rejection of PEG600 all higher than 90%; The flux of beta cyclodextrin film to isopropyl alcohol, ethyl acetate, butanone and normal heptane is respectively 37.2,18.6,17.3 and 25.3L ﹒ m
-2﹒ h
-1the flux 3.50L ﹒ m of toluene
-2﹒ h
-1.
Embodiment 3
Select the polyacrylonitrile ultrafiltration film of molecular cut off 200,000, the method described according to embodiment 2 and step masking, but the cyclodextrin dissolved in aqueous phase solution is γ cyclodextrin, its consumption is identical with embodiment 2.Institute's masking is designated as γ cyclodextrin film.
γ cyclodextrin film area swellbility in isopropyl alcohol, ethyl acetate, butanone, normal heptane and toluene is less than 4.5%, and thermogravimetric analysis (TGA) shows that the initial degradation temperature of film is 328.1 DEG C, and namely film has good heat endurance.Under room temperature and 1MPa condition, γ cyclodextrin film to the rejection of PEG4000 higher than 90%; The flux of γ cyclodextrin film to isopropyl alcohol, ethyl acetate, butanone and normal heptane is respectively 44.6,27.6,24.1 and 48.1L ﹒ m
-2﹒ h
-1, the flux of toluene reaches 25.6L ﹒ m
-2﹒ h
-1.
Embodiment 4
Select the polyacrylonitrile ultrafiltration film of molecular cut off 50,000, the method described according to embodiment 2 and step masking, but add m-phenylene diamine (MPD) and polyepichlorohydrin amine in aqueous phase, addition is 1% of solution weight, in organic phase solution, add pyromellitic trimethylsilyl chloride and m-phthaloyl chloride, pyromellitic trimethylsilyl chloride addition is 2% of solution weight; M-phthaloyl chloride addition is 2% of solution weight.
Made beta cyclodextrin film has good solvent resistance and heat endurance equally.In isopropyl alcohol, ethyl acetate, butanone, normal heptane and toluene, area swellbility is less than 4.5%, and thermogravimetric analysis (TGA) shows that the initial degradation temperature of film is 327.5 DEG C, and namely film has good heat endurance.Under room temperature and 1MPa condition, this film to the rejection of PEG1000 higher than 90%; 42.6,30.8,28.4 and 43.1L ﹒ m are respectively to the flux of isopropyl alcohol, ethyl acetate, butanone and normal heptane
-2﹒ h
-1, the flux of toluene is 9.7L ﹒ m
-2﹒ h
-1.
Claims (6)
1. a cyclo-dextrin-modified compounded organic solvent NF membrane, is characterized in that: be prepared from by the following method:
(1) polyacrylonitrile ultrafiltration film being immersed into concentration is 0.3 ~ 2.5mol ﹒ L
-1sodium hydrate aqueous solution in, submergence reaction at 30 ~ 80 DEG C, take out subsequently and in deionized water fully washing obtain the polyacrylonitrile ultrafiltration film that is hydrolyzed;
(2) add in deionized water by cyclodextrin, at room temperature ultrasonic process is to being uniformly dispersed; Again aminated compounds is joined in above-mentioned cyclodextrin aqueous solution, continue to be stirred to and evenly obtain aqueous phase solution; Wherein aminated compounds addition is 1% ~ 5% of solution weight; Cyclodextrin addition is 0.01% ~ 0.2% of solution weight; Described aminated compounds is the one of polymine, m-phenylene diamine (MPD), piperazine and polyepichlorohydrin amine, or the mixture of two kinds of compounds;
(3) cast on the polyacrylonitrile ultrafiltration film after hydrolysis process by aqueous phase solution, remove aqueous phase solution after soaking at room temperature, under room temperature, drying makes face remove moisture;
(4) acyl chloride compound is dissolved in hexane solution and obtains organic phase solution, wherein acyl chloride compound addition is 1% ~ 5% of solution weight; Described acyl chloride compound refers to the one of pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, or the mixture of two kinds of compounds;
(5) organic phase solution is cast on the basement membrane of step (3) gained, react under room temperature, after reaction terminates, remove organic phase solution;
(6) basement membrane being compounded with interfacial polymerization layer is taken out, be placed in vacuum constant temperature drying box and heat-treat, obtain cyclo-dextrin-modified compounded organic solvent NF membrane.
2. cyclo-dextrin-modified compounded organic solvent NF membrane as claimed in claim 1, is characterized in that: described polyacrylonitrile ultrafiltration film molecular cut off is 1 ~ 200,000.
3. cyclo-dextrin-modified compounded organic solvent NF membrane as claimed in claim 1 or 2, it is characterized in that: described cyclodextrin is α cyclodextrin, beta cyclodextrin or γ cyclodextrin, corresponding obtained alpha-cyclodextrin NF membrane respectively, beta-schardinger dextrin-NF membrane, gamma-cyclodextrin NF membrane.
4. prepare the method for cyclo-dextrin-modified compounded organic solvent NF membrane according to claim 1, it is characterized in that: realize by the following method:
(1) polyacrylonitrile ultrafiltration film being immersed into concentration is 0.3 ~ 2.5mol ﹒ L
-1sodium hydrate aqueous solution in, submergence reaction at 30 ~ 80 DEG C, take out subsequently and in deionized water fully washing obtain the polyacrylonitrile ultrafiltration film that is hydrolyzed;
(2) add in deionized water by cyclodextrin, at room temperature ultrasonic process is to being uniformly dispersed; Again aminated compounds is joined in above-mentioned cyclodextrin aqueous solution, continue to be stirred to and evenly obtain aqueous phase solution; Wherein aminated compounds addition is 1% ~ 5% of solution weight; Cyclodextrin addition is 0.01% ~ 0.2% of solution weight; Described aminated compounds is the one of polymine, m-phenylene diamine (MPD), piperazine and polyepichlorohydrin amine, or the mixture of two kinds of compounds;
(3) cast on the polyacrylonitrile ultrafiltration film after hydrolysis process by aqueous phase solution, remove aqueous phase solution after soaking at room temperature, under room temperature, drying makes face remove moisture;
(4) acyl chloride compound is dissolved in hexane solution and obtains organic phase solution, wherein acyl chloride compound addition is 1% ~ 5% of solution weight; Described acyl chloride compound refers to the one of pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, or the mixture of two kinds of compounds;
(5) organic phase solution is cast on the basement membrane of step (3) gained, react under room temperature, after reaction terminates, remove organic phase solution;
(6) basement membrane being compounded with interfacial polymerization layer is taken out, be placed in vacuum constant temperature drying box and heat-treat, obtain cyclo-dextrin-modified compounded organic solvent NF membrane.
5. the preparation method of cyclo-dextrin-modified compounded organic solvent NF membrane as claimed in claim 4, is characterized in that: described polyacrylonitrile ultrafiltration film molecular cut off is 1 ~ 200,000.
6. the preparation method of the cyclo-dextrin-modified compounded organic solvent NF membrane as described in claim 4 or 5, is characterized in that: described cyclodextrin is α cyclodextrin, beta cyclodextrin or γ cyclodextrin.
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