CN109745873A - High transmission and highly selective PVA/GA/CS-M+ pervaporation film for organic solution dehydration - Google Patents
High transmission and highly selective PVA/GA/CS-M+ pervaporation film for organic solution dehydration Download PDFInfo
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Abstract
The present invention relates to a kind of high transmission for organic solution dehydration and highly selective pervaporation films and preparation method thereof, with Ag+、Cu2+、Fe3+Etc. heavy metal ion (M+) CS (chitosan) is chelated as precursor, blending is carried out with PVA (polyvinyl alcohol), GA (glutaraldehyde) is added as crosslinking agent, can be formed with high mechanical strength, thermal stability and the PVA/GA/CS-M that can express excellent permeability and selectivity to the dehydration of organic solution+Pervaporation film.
Description
Technical field
The present invention particularly relates to a kind of high transmission and height for organic solution dehydration about a kind of pervaporation film
The pervaporation film and preparation method thereof of selectivity.
Background technique
Isopropanol (Isopropanol, IPA) can be used for producing the raw materials such as acetone, isopropyl ester, isopropylamine, be also widely used in
Pharmacy, pesticide, cosmetics, plastics, fragrance, coating etc., and as the detergent and oil, natural gum, wax and cosmetics in semiconductor
Equal solvent.Ethyl alcohol (Ethanol, EtOH) may be utilized in fabricating acetic acid, acetaldehyde, ether, ethyl acetate, ethamine etc., and produce doctor
The raw material of the products such as medicine, cosmetics, dyestuff, coating, detergent, beverage, essence, vehicle fuel.Acetone (Acetone) is removed and is used for
Manufacture bisphenol-A, methyl methacrylate, acetone cyanohydrin, outside the products such as methyl iso-butyl ketone (MIBK), be equally applicable for medicine, cosmetics,
Building materials, paint, plastics, fiber, gunpowder, resin, rubber, photographic roll film etc..Reusing for organic solvent significantly helps
In economic advantages and environmental protection, the dehydration of organic solvent is caused to be even more important in the development of thin film technique.Utilize pervaporation
Film is more superior than traditional distillating method to separate alcohol/aqueous mixtures, because it can overcome alcohol/water azeotropism.It is special
It is not, due to not needing to operate at high temperature, so pervaporation thin film separation is energy-efficient effective technique.
Solubility-diffusion model is received to describe the transport phenomena in pervaporation thin film technique far and away.Institute
The structure for stating film can greatly influence dissolution-dispersal behavior of solution, to influence transmission efficiency.
Lu etc. propose the hydration of film in process of pervaporation and show as include the attached balance of absorption-desorption dynamic mistake
Journey.Be easy to be absorbed since hydrophilic film can make water-spread, therefore transmission efficiency can be promoted.Therefore, the water suction of hydrophilic film
Performance becomes the key factor of pervaporation separating film design.
PVA is the high-hydrophilic polymer with good filming and chemical resistance, it has also become one kind is used for pervaporation
The preferred material of dehydration.However, due to the presence of its hydroxyl, so that it is difficult to be blanked containing the Swelling in water-soluble night.
By introducing crosslinked agent, the intermolecular structure of PVA basement membrane can be enhanced stronger covalent bond between polymer chain and be formed, rather than
Weaker hydrogen bond, and then mechanical strength is improved, and greatly increase stability.The pervaporation test is to evaluate
The pervaporation separation efficiency of film, and measured according to contact angle, degrees of expansion, mechanical performance and thermal stability obtained
The physicochemical properties of film.Though it can consume the hydrophilic of macromolecular chain however, crosslinking agent can make the structure of film relatively stable
Group, it is known that more stable membrane structure can be formed to PVA matrix through crosslinking agent, negative shadow can be also brought in terms of water penetration
It rings, reason is that the formation of crosslinking agent can consume hydroxyl in PVA polymer.Therefore, pervaporation film how is improved, it is made
It can be used for the dehydration of organic solution, and the transmitance of water can be effectively facilitated, do not lose its selectivity, be in fact urgent need to resolve instantly
Project.
Summary of the invention
The purpose of the present invention provide it is a kind of for organic solution dehydration high transmission and highly selective pervaporation it is thin
Film and preparation method thereof.
To achieve the above object, high transmission and highly selective pervaporation of the present invention for organic solution dehydration
The preparation method of film comprising the following steps:
Prepare material: preparing the glutaraldehyde (GA) and 99 weights of polyvinyl alcohol (PVA), chitosan (CS), 25 weight percent
Measure isopropanol, ethyl alcohol and the acetone of percentage；
Prepare polyvinyl alcohol, chitosan and glutaraldehyde；
The polyvinyl alcohol of one Unit Weight is dissolved in the deionized water of nine Unit Weights, stirs 20 under the conditions of 70 DEG C
~24 hours, form liquid B；
The liquid A and the liquid B are sufficiently mixed and stirs at least 2 hours and forms mixed solution C；
It stirs at least 1 hour, which is placed in the culture dish of polyethylene material, in an oven at 70 DEG C
Being dried 1 day with 25 DEG C -50 DEG C of temperature and glutaraldehyde is added can be used for what the high selection that the organic solution is dehydrated penetrated to be formed
Pervaporation film.
Further, wherein the organic solution be the isopropanol water solution of 99wt%, ethanol water, aqueous acetone solution or
Other aqueous solutions of organic solvent.
Further, wherein a Unit Weight is 5g, which is 45g.
Further, the time that is stirred at room temperature that wherein chitosan is dissolved in ionized water is 8 hours, which is dissolved in deionization
The mixing time of water is 24 hours.
Further, wherein the silver ion or copper ion or when iron ion of higher concentration is added, can obtain have it is more uniform
Reticular structure film, this indicates that the silver ion of CS chelating or copper ion or iron ion and PVA interact, to improve CS
With the compatibility of PVA.
Further, wherein the concentration of the glutaraldehyde is 25wt%, and the crosslinked action that glutaraldehyde generates is added, makes the infiltration
Thin evaporated film can play optimal thermal stability.
Further, wherein Ag+Or Cu2+Or Fe3+Or other heavy metal ion chelating CS is to promote the pervaporation thin
The intermolecular interaction of film, and then the high polymeric matrix of compatibility is obtained, and can be mixed in water/organic solvent system
It closes in object and absorbs more water, and make its own swelling without losing its reticular structure.
In addition, the present invention also provides a kind of pervaporation films formed according to above-mentioned preparation method.
Invention further provides it is a kind of for the high selection of dehydration of organic solvent and the pervaporation of high-permeability it is thin
Film using glutaraldehyde as polyvinyl alcohol and the crosslinking agent of chitosan, and is added silver ion or copper ion or iron ion and is formed.
The invention has the following advantages:
Pervaporation film prepared by the present invention has high mechanical strength, thermal stability and the dehydration to organic solution
It can express excellent permeability and selectivity；Its transmitance that can be effectively facilitated water, without losing its selectivity.
Detailed description of the invention
Fig. 1 shows (a) pure PVA, (b) pure CS, (c) PVA/CS, (d) PVA/CS-Ag+(Ag+: 1.17x10-1Mol.) and
(e)PVA/GA/CS-Ag+(Ag+: 1.17x10-1Mol. FTIR spectrum figure).
Fig. 2 is to include (a) pure PVA, (b) pure chitosan, (c) PVA/CS, (d) PVA/CS-Ag+(Ag+: 1.17x10- 1Mol.), (e) PVA/GA/CS-Ag+(Ag+: 1.17x10-1Mol. TGA figure).
Fig. 3 is shown with different content Ag+PVA/GA/CS-Ag+The contact angle of pervaporation film.
Fig. 4 is water concentration in water/isopropanol mixture to different Ag+The PVA/GA/CS-Ag of content+The shadow of membrane swelling degree
It rings.
Fig. 5 is to have different content Ag at 30 DEG C+PVA/GA/CS-Ag+Pervaporation film, in various water/isopropyls
The transit dose of alcohol mixture.
Fig. 6 is shown through PVA/GA/CS-Ag+At 30 DEG C, (it is pure and strong that 90 weight percent feed isopropyl to pervaporation film
Degree) under, Ag+Content influences water/isopropanol mixture pervaporation efficiency.
Fig. 7 is to have different content Cu at 30 DEG C2+PVA/GA/CS-Cu2+Pervaporation film, in various water/different
The transit dose of propanol mixture.
Fig. 8 is to have different content Fe at 30 DEG C3+PVA/GA/CS-Fe3+Pervaporation film, in various water/different
The transit dose of propanol mixture.
Fig. 9 is to have different content Ag at 30 DEG C+PVA/GA/CS-Ag+Pervaporation film, in various water/ethyl alcohol
The transit dose of mixture.
Figure 10 is the PVA/GA/CS-Ag+ pervaporation film at 30 DEG C with different content Ag+, in various water/the third
The transit dose of alcohol/ketone mixtures.
Figure 11 is to have different content Cu at 30 DEG C2+PVA/GA/CS-Cu2+Pervaporation film, in various water/second
The transit dose of alcohol mixture.
Figure 12 is to have different content Cu at 30 DEG C2+PVA/GA/CS-Cu2+Pervaporation film, in various water/the third
The transit dose of alcohol/ketone mixtures.
Figure 13 is to have different content Fe at 30 DEG C3+PVA/GA/CS-Fe3+Pervaporation film, in various water/second
The transit dose of alcohol mixture.
Figure 14 is to have different content Fe at 30 DEG C3+PVA/GA/CS-Fe3+Pervaporation film, in various water/the third
The transit dose of alcohol/ketone mixtures.
Figure 15 a~h is to include (a) pure PVA, (b) PVA/CS, (c) PVA/GA/CS-Ag+ (Ag:2.4x10-2Mol.), (d)
PVA/GA/CS-Ag+(Ag+: 4.7x10-2Mol.), (e) PVA/GA/CS-Ag+ (Ag+: 7.1x10-2Mol.), (f) PVA/GA/
CS-Ag+(Ag+: 9.4x10-2Mol.), (g) PVA/GA/CS-Ag+(Ag+: 1.17x10-1Mol.) the SEM figure and (h) EDS of film
Scheme (Ag+: 1.17x10-1mol.)。
Figure 16 a~e is to include (a) PVA/GA/CS-Cu2+(1.9x10-2mol.Cu2+), (b) PVA/GA/CS-Cu2+
(3.7x10-2mol.Cu2+), (c) PVA/GA/CS-Cu2+(5.6x10-2mol.Cu2+), (d) PVA/GA/CS-Cu2+(7.5x10-
2mol.Cu2+) and (e) PVA/GA/CS-Cu2+(9.3x10-2mol.Cu2+) film SEM figure.
Figure 17 a~e is to include (a) PVA/GA/CS-Fe3+(1x10-2mol.Fe3+), (b) PVA/GA/CS-Fe3+(2x10- 2mol.Fe3+), (c) PVA/GA/CS-Fe3+(3x10-2mol.Fe3+), (d) PVA/GA/CS-Fe3+(4x10-2mol.Fe3+) and
(e)PVA/GA/CS-Fe3+(5x10-2mol.Fe3+) film SEM figure.
Figure 18 a-1~a-2 is that the AFM of pure PVA film schemes.
Figure 19 a~c be include (a-1~a-2) CS/PVA ratio be 1/5, (b-1~b-2) CS/PVA ratio be 3/5, (c-
1~c-2) CS/PVA ratio be 5/5 different CS/PVA weight ratio films AFM figure.
Figure 20 a~c be include (a-1~a-2) Ag+: 2.4x10-2Mol., (b-1~b-2) Ag+: 7.1x10-2Mol, (c-1
~c-2) Ag+: 1.17x10-1Mol. difference Ag+The PVA/GA/CS-Ag of additive amount+The AFM of film schemes.
Figure 21 a~c be include (a-1~a-2) Cu2+: 1.9x10-2mol.Cu2+, (b-1~b-2) Cu2+: 5.6x10- 2mol.Cu2+, (c-1~c-2) Cu2+: 9.3x10-2Mol. difference Cu2+The AFM of the PVA/GA/CS-Cu2+ film of additive amount schemes.
Figure 22 a~c be include (a-1~a-2) Fe3+: 1x10-2Mol., (b-1~b-2) Fe3+: 3x10-2Mol., (c-1~
C-2) Fe3+:5x10-2Mol. difference Fe3+The PVA/GA/CS-Fe of additive amount3+The AFM of film schemes.
Specific embodiment
The present invention is further explained in the light of specific embodiments, so that those skilled in the art can be better
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
The present invention provides it is a kind of for organic solution dehydration high-permeability and highly selective pervaporation film and
Preparation method, which comprises
Preparation material: polyvinyl alcohol (PVA) (Mw~125,000), chitosan (CS) (Mw~30,000), the penta of 25wt%
The isopropanol (IPA) of dialdehyde (GA) and 99wt%, ethyl alcohol (EtOH) and acetone (Acetone).All chemical reagent are examination
Medicine grade, and be not required to be further purified.
Preparation process: the CS of 5g is dissolved in 45g deionized water, is stirred at room temperature 7~10 hours, was preferred especially with 8 hours, so
The silver of different weight, copper, iron ion, that is, Nitrates are added in previous solution respectively afterwards, form liquid A, and continue
Stirring, in other words, the CS of liquid A and the weight ratio of deionized water are 1: 9.5g PVA is dissolved in 45g deionized water, at 70 DEG C
Under the conditions of stir 20~24 hours, be preferred especially with 24 hours, formed liquid B, in other words, the PVA of liquid B and the weight of deionized water
Amount is than being 1: 9.Liquid A and B are sufficiently mixed and stir 2 hours and form mixed solution C.Then mixed solution C is poured by gathering
In an oven with 1 day dry under 40 DEG C of assigned temperature in culture dish made of ethylene, and glutaraldehyde is added and forms PVA/GA/
CS-M+ (M+ indicates heavy metal ion) pervaporation film, wherein the temperature of the baking oven is unsuitable too high or too low, in order to avoid influence this
The formation of contrivance.
Pervaporation film obtained by the present invention will do it the survey such as contact angle, swellbility, mechanical performance and thermal stability
Amount.In addition, pervaporation film of the invention can identify object of the present invention through Fourier Transform Infrared Spectroscopy (FTIR) analysis respectively
Functional group, be described as follows described.
Fourier Transform Infrared Spectroscopy (FTIR): the mirror of the functional group of the pervaporation film and their interaction
Fixed system shows through FTIR spectrum (Perkin-Elmer spectrometer, FTS-1000).In wavelength zone 450-
4000cm-1It is measured in infrared spectral region.
Thermogravimetric analysis (TGA, Thermogravimetric analysis): in the case where being oxygenated environment, sweep speed be 10 DEG C/
Under the sweep speed of min, TGA test is carried out using Perkin-Elmer Pyis-17GA, Range of measuring temp is 25-800 DEG C.
Scanning electron microscope and energy dispersion spectrometry (SEM&EDS): observation film is carried out using scanning electron microscope
Configuration of surface, and the energy dispersive spectrum for studying composition.
Atomic force microscope is used to detect the roughness and microscopic surface texture of film.
Contact angle: specimen surface shows pervaporation film by contact angle analyzer (FTA125 contact angle analyzer)
Chemical and physical features feature.The contact angle of water is placed on pervaporation film surface by will distill water droplet and carries out.
Swellbility: object of the present invention obtained is cut into 2cm × 2cm sample, is placed in precision balance (Ab304-S/FACT)
To obtain its weight (Wd, the weight of dry film), dry film is put into water/isopropanol mixture of the various ratios of 100g and is kept respectively
After 24 hours, then with the weight (Ws) of precision balance acquisition wet film.The swellbility of film is calculated by following formula (1):
Pervaporation experiment: pervaporation dehydration measurement is carried out in equipment as described above.It is measured by mercury pressure
Feed zone pressure is measured, and pressure is maintained to the vacuum degree of about 2 support ears (torr) using vacuum pump, is contacted with incoming mixture
Effective area is about 7cm2, and by automatically controlled thermometer the feeding temperature of mixture is maintained at 30 DEG C.With refractometer (RX-
5000 α) measure the composition for penetrating object.The pervaporation separation efficiency of object of the present invention is according to transit dose and separation factor (α sep)
To assess.
Wherein W is the quality (kg) through object, and A is the effective area (m2) of pervaporation film, and t is the time penetrated
(h), Pw and PIPA, PEtOH, PAcetone are respectively the mass percent for penetrating end water and isopropanol, ethyl alcohol, acetone etc..Fw,
FIPA, FEtOH, FAcetone are respectively the mass percent of water, isopropanol, ethyl alcohol, acetone etc. in feeding.By aforementioned every real
Acquired results are tested, can be further illustrated by following analysis.
FTIR analysis: Fig. 1 is shown including PVA (a), CS (b), PVA/CS (c), PVA/CS-Ag+(d) and PVA/GA/CS-
Ag+(e) the FT-IR spectrogram of pervaporation film, wherein in 3100-3500cm-1Place is presented wide absorption band and is attributed to-OH
Stretching vibration.In 2833,1324 and 843cm-1Peak it is corresponding be C-H stretching and C-H bending.1086,
1415,1719cm-1Peak can be accredited as-C-O group.In the map of chitosan, 1570-1655cm-1Characteristic absorption
Band is attributed to amide I, II and-C=O group.1077,1320 and 1154cm-1Peak respectively represent the flexible and glycosyl of C-O-N
Group.PVA/GA/CS-Ag+1719cm-1The peak at place is less than the peak of (a), (c) and (d) same position, indicate GA and film it
Between have interaction.Therefore it can determine whether the formation for having acetal (C-O-C) key in PVA/GA/CS-Ag+ film.
TGA analysis: PVA, CS, PVA/CS, PVA/CS-Ag+And PVA/GA/CS-Ag+Thermogravimetric analysis map such as Fig. 2 institute
Show.(heat resistance of film can be significantly increased in curve d), use the crosslinked action (curve of glutaraldehyde for the importing of its proof silver ion
E), the optimal thermal stability of film can more be played.
SEM form & elemental analysis: observation Figure 15 a~h, Figure 16 a~e and Figure 17 a~e, when be added high level silver from
When son, copper ion or iron ion, agglomerate phenomenon caused by pervaporation film obtained is mixed without PVA with CS has simultaneously
There is rougher reticular structure, shows with Ag+、Cu2+、Fe3+Etc. the presence of CS of heavy metal ion chelating can promote PVA/GA/
CS-M+The intermolecular interaction of pervaporation film, to improve its compatibility.
AFM AFM Analysis: pure PVA film surface known to observation Figure 18 and Figure 19 a~c is more smooth, when mixed
When the more CS is added, biggish agglomerate will cause.It can be found by Figure 20 a~c, Figure 21 a~c and Figure 22 a~c, with Ag+、Cu2 +、Fe3+Etc. heavy metal ion increase, the agglomerate of film surface gradually becomes smaller, and the roughness of film surface also gradually increases, with
The test result of SEM is consistent.
Contact angle research: measurement different content Ag+PVA/GA/CS-Ag+The water contact angle of pervaporation film.Observation knot
Fruit is as shown in figure 3, display contact angle is reduced as silver ion content increases.This is highly polar because silver ion has, therefore at it
In the presence of, PVA/GA/CS-Ag+Pervaporation film hydrophily with higher.
Swellbility: in the present invention, will be with Ag+、Cu2+、Fe3+It is blended Deng the chitosan chelated through heavy metal ion with PVA,
Then the pervaporation film to be formed for organic water-soluble fluid dewatering is reacted with glutaraldehyde cross-linking.In general, crosslinking agent is available
In preventing polymer substrate to be swollen because of water suction, but this will lead to the reduction of hydrophilic nmature, and reduce the flux of dehydration.By
In chitosan, it is present in the unshared electron pair in ammonia nitrogen, can adsorb heavy metal ion by chelating, make film
Polarity promoted and greatly increase the water imbibition of film.Fig. 4 is water concentration in water/isopropanol mixture to different content Ag+'s
PVA/GA/CS-Ag+The influence of membrane swelling degree, the results show that the PVA/GA/CS-Ag of higher silver ion content+Pervaporation film
With use higher water/isopropanol ratio aqueous solution, pervaporation film reflects the Percent expansion of higher degree.The present invention
It was found that with Ag+、Cu2+、Fe3+Etc. the presence of CS of heavy metal ion chelating can promote PVA/GA/CS-M+Point of pervaporation film
It interacts between son, so that the polymeric matrix of preferable compatibility is obtained, it can be in water/organic solvent mixture
More water are absorbed, and make its own expansion without losing its reticular structure.
PVA/GA/CS-Ag with different content silver ion+The pervaporation that film seeps is dehydrated efficiency: at 30 DEG C, benefit
With the PVA/GA/CS-Ag with the silver ion of different content chelating+It is dehydrated that film carries out water/aqueous isopropanol pervaporation
Journey.The results show that silver ion chelates more films, the transmitance of presentation is higher.This is caused polar because of the addition of silver ion
Increase.Fig. 4 is compared with Fig. 5, both find the result is that similar.In Fig. 4, the promotion of degree of swelling is mainly due to
The increase of water content；However, the chelating of silver ion can also promote the effect.Similarly, more water contents can be brought in charging
Higher transit dose, improves the content of silver ion, and transit dose (such as Fig. 5) has also been significantly increased.Our available conclusions, i.e.,
It is sequestered in the importance for the dehydration that the silver ion on CS molecule is especially shown for aqueous isopropanol in low water content charging,
Importance is also reflected in very high water penetrating concentration shown in fig. 6.No matter how many silver ion are introduced to prepare PVA/GA/CS-
Ag+Pervaporation film can reach 99.99% through end water concentration, and wherein concentration of silver ions is 1.17 × 10-1Mol., water
Transit dose is even up to 2kg/m2h。
The present invention is compared with given data: using using PVA as the pervaporation film of matrix, for aqueous isopropanol
Dehydration, with the charging of 10 weight percent at 30 DEG C, the results are shown in Table 1.In general, when selection is than increasing, thoroughly
Excessive present reduces.The present invention is using GA as crosslinking agent, with Ag+、Cu2+、Fe3+Etc. heavy metal ion chelating CS be precursor, it is right
It is all greatly improved in selection ratio and transit dose.With silver ion content for 1.17 × 10-1mol., the water of 10 weight % is fed,
It can reach the high separating efficiency of the separation factor with up to 89991.
Table 1: to the separation efficiency for modifying PVA pervaporation film reported in the known references for isopropanol dehydration
Research is compared.
PVA, it is poly- (vinyl alcohol)；CA, citric acid；AA, amic acid；USF, urea-formaldehyde/sulfuric acid；CS, chitosan；GA, penta
Dialdehyde；NaAlg, sodium alginate
It illustrates, according to the method for aforementioned pervaporation membrane-film preparation process of the present invention, wherein silver ion can be replaced
Copper ion, iron ion or other heavy metal ion are changed to, remaining method is identical, and then can form PVA/GA/CS-Cu2+Or PVA/
GA/CS-Fe3+(with PVA/GA/CS-M+It indicates, wherein M+Indicate heavy metal ion) pervaporation film, physical characteristic is as drawn
Intensity is stretched to be described as follows:
Tensile strength: PVA/CS, PVA/CS-Ag are evaluated according to the measurement of tensile strength+, PVA/GA/CS-Ag+, PVA/
GA/CS-Cu2+And PVA/GA/CS-Fe3+The mechanical property of pervaporation film, test data are listed in Table 2 below.Work as chitosan
When being blended in PVA, can almost double to improve tensile strength, display PVA and CS good compatibility, and between there are powerful mutual
Effect.As introducing Ag+In film, the tensile strength of film can be significantly increased, even if in the case where not adding crosslinking agent, through Ag+Chela
The intermolecular of the CS and PVA of conjunction has very important interaction force, this facilitates compatibility more preferably polymeric matrix
It is formed.Chelate Ag+CS in addition to the separation efficiency that can greatly improve organic water-soluble night, the machinery of polymeric matrix also can be improved
Intensity.This can penetrate PVA/GA/CS and PVA/GA/CS-Ag+The comparison of pervaporation film illustrates, wherein silver ion
Introducing can greatly improve tensile strength up to 64.7%, display and Ag+Strong interaction between the CS and PVA of chelating, this also may be used
Reflect the improvement of heat-resisting property.In addition it can be seen that addition copper ion and iron ion also show the similar addition of generation by the data of table 2
The result and characteristic of silver ion.
Table 2: the tensile strength and tensile elongation of pervaporation film
And PVA/CS, PVA/CS-Ag are evaluated in terms of pervaporation experiment+、PVA/GA/CS-Ag+、PVA/GA/CS-
Cu2+And PVA/GA/CS-Fe3+Film, can be respectively by every the results show of figure 5-8, Cu2+、Fe3+Addition with plus
Enter the same transit dose that can be effectively facilitated water of Ag+, without losing its selectivity.In addition, pervaporation film of the invention removes
It is suitable for isopropanol water solution, also can be used for the dehydration of ethanol water and aqueous acetone solution, it can by the reality of Fig. 9-Figure 14
Test result explanation.This also shows that the popularity for all having application for the dehydration of numerous organic solution.
In conclusion the present invention chelates before CS is respectively by crosslinking agent and silver ion, copper ion and iron ion etc. of GA
Body is blended with PVA, can successfully prepare PVA/GA/CS-Ag+、PVA/GA/CS-Cu2+And PVA/GA/CS-Fe3+Equal pervaporations
Film.The present invention is used for the dehydration of organic solution, has good mechanical property and heat resistance.The present invention is fed at 30 DEG C to be had
Machine solution forms pervaporation film using introducings such as silver ion, copper ion, iron ions, can be effectively facilitated the infiltration speed of water
Rate, without losing its selectivity.For example, the present invention is with Ag+Content is 1.17 × 10-1Mol. film, through detection learn,
It is the dehydration of the high concentration aqueous isopropanol of 90 weight percent for concentration at 30 DEG C, may be implemented with up to 89991
Separation factor, and up to 2kgm2The transit dose of h；And known technology uses the pervaporation using PVA as matrix under some circumstances
Film, the results are shown in Table 1, it is however generally that, when transit dose increases, selectivity, which is presented, to be reduced, it can thus be appreciated that of the invention
Excellent place.Particularly, the present invention also shows the validity of the dehydration fed under lower water content, is conducive to large-scale
Purification application.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (9)
1. a kind of exist for the high transmission of organic solution dehydration with the preparation method of highly selective pervaporation film, feature
In, including the following steps:
Prepare polyvinyl alcohol, chitosan and glutaraldehyde；
The chitosan of one Unit Weight is dissolved in the deionized water of nine Unit Weights, is stirred at room temperature 7~10 hours, to shape
At a solution；
Silver ion or copper ion or iron ion salt are added in the solution, to form liquid A, and continue to stir；
The polyvinyl alcohol of one Unit Weight is dissolved in the deionized water of nine Unit Weights, 20~24 are stirred under the conditions of 70 DEG C
Hour, form liquid B；
The liquid A and the liquid B are sufficiently mixed and stirs at least 2 hours and forms mixed solution C；
It stirs at least 1 hour, which is placed in the culture dish of polyethylene material, in an oven with 25 at 70 DEG C
Simultaneously glutaraldehyde is added to form the infiltration that can be used for the high selection of organic solution dehydration and penetrate in dry 1 day of DEG C -50 DEG C of temperature
Thin evaporated film.
2. preparation method as described in claim 1, which is characterized in that the organic solution be 99wt% isopropanol water solution,
Ethanol water, aqueous acetone solution or other aqueous solutions of organic solvent.
3. preparation method as described in claim 1, which is characterized in that a Unit Weight is 5g, which is
45g。
4. preparation method as described in claim 1, which is characterized in that the time that is stirred at room temperature that the chitosan is dissolved in ionized water is
8 hours, the mixing time which is dissolved in deionized water was 24 hours.
5. preparation method as described in claim 1, which is characterized in that be added higher concentration silver ion or copper ion or iron from
The period of the day from 11 p.m. to 1 a.m can obtain the film with more uniform reticular structure, this indicate the silver ion of CS chelating or copper ion or iron ion with
PVA interaction, to improve the compatibility of CS and PVA.
6. preparation method as described in claim 1, which is characterized in that the concentration of the glutaraldehyde is 25wt%, and glutaraldehyde is added
The crosslinked action of generation enables the pervaporation film to play optimal thermal stability.
7. preparation method as described in claim 1, which is characterized in that Ag+Or Cu2+Or Fe3+Or other heavy metal ion chelating
CS obtains the high polymeric matrix of compatibility, and make it to promote the intermolecular interaction of the pervaporation film
More water can be absorbed in water/organic solvent system mixture, and make its own swelling without losing its reticular structure.
8. a kind of pervaporation film that preparation method according to claim 1 is formed.
9. a kind of for the high selection of dehydration of organic solvent and the pervaporation film of high-permeability, which is characterized in that it is with penta
Dialdehyde is added silver ion or copper ion or iron ion and is formed as polyvinyl alcohol and the crosslinking agent of chitosan.
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| CN103157299A (en) * | 2013-03-26 | 2013-06-19 | 清华大学 | Oil-water separation mesh film with acid-base salt stabilizing function and with underwater super-oleophobic property and preparation method thereof |
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| CN104014259A (en) * | 2014-05-27 | 2014-09-03 | 中国科学院过程工程研究所 | Preparation method of hydrophobic separating membrane |
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