CN108126534A - The filling of APTS modified carbon blacks PIM-1 composite membranes and preparation method isolate and purify n-butanol method - Google Patents
The filling of APTS modified carbon blacks PIM-1 composite membranes and preparation method isolate and purify n-butanol method Download PDFInfo
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- CN108126534A CN108126534A CN201711461472.7A CN201711461472A CN108126534A CN 108126534 A CN108126534 A CN 108126534A CN 201711461472 A CN201711461472 A CN 201711461472A CN 108126534 A CN108126534 A CN 108126534A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention provides a kind of filling of APTS modified carbon blacks 1 composite membranes of PIM and preparation method, isolates and purifies n-butanol method, is related to infiltration evaporation technical field of membrane.The compound membrane preparation method is：With 3 aminopropyl triethoxysilanes (APTS) modified carbon black, using modified carbon black nano-particle as filler, it is added in soluble intrinsic microporous polymer (PIM 1) matrix, using cellulose acetate as supporting layer, tablet osmosis vaporizing compound membrane is prepared for, this composite membrane can efficiently separate purifying butanol solution, the hydrophobicity of composite membrane is strong, infiltration evaporation performance is good, which can have very high n-butanol separating capacity while high permeating flux is ensured.
Description
Technical field
The present invention relates to a kind of infiltration evaporation technical field of membrane, and more particularly to a kind of APTS modified carbon blacks filling PIM-1
Composite membrane and preparation method isolate and purify n-butanol method.
Background technology
With the aggravation of energy crisis and the environmental pollution of getting worse, pass is increasingly caused for the exploitation of clean energy resource
Note.N-butanol is a kind of important industrial chemicals, and is expected to as the bio-fuel of a new generation, using reproducible biomass fermentation
Ferment prepares n-butanol and receives more and more attention.N-butanol can be added to very high ratio in gasoline, greatly improve vapour
The efficiency of combustion of oil, while n-butanol burning only can generate carbon dioxide and water, not can cause environmental pollution.Since fermentation is produced
Object butanol has toxicity inhibition effect to fermenting microbe, causes fermentation method to be used to prepare the inefficient of biological butanol at present, not have
It is widely used.At present using conventional distillation method separating butanol, way of distillation separative efficiency is low, and exists a large amount of
Fuel energy consumption, while additional pollution can be caused during fuel combustion, be difficult to realize industrialized production.
Compared to the way of distillation, infiltration evaporation membrane separation technique has the advantages that separation selectivity is good, low energy consumption, free of contamination.
Infiltration evaporation and fermentation method are used in conjunction, n-butanol separative efficiency can be significantly increased, and not can cause environmental pollution.Specially
Sharp CN103877874A discloses a kind of preparation method of dimethyl silicone polymer-carbon nano-tube compound film, its composite membrane and divides
Method from purified butanol, by adding in carbon nanotube in dimethyl silicone polymer, although improving to a certain extent point
From the permeation flux and separation factor during butanol, but separative efficiency promotion is limited, and the cost of carbon nanotube is higher.
Invention content
The purpose of the present invention is to provide a kind of preparation method of APTS modified carbon blacks filling PIM-1 composite membranes, this preparations
Method is simple, easy to operate, suitable for industrialized production.
Another object of the present invention is to provide a kind of APTS modified carbon blacks filling PIM-1 composite membranes, by by Modified Activated Carbon
Black nano-particle is added in PIM-1 matrixes, obtains composite membrane while high permeating flux is ensured, has very high butanol point
From ability.
Third object of the present invention is to provide a kind of method for isolating and purifying n-butanol, using above-mentioned composite membrane point
From purifying butanol solution, excellent.
The present invention is solved its technical problem and is realized using following technical scheme.
The present invention proposes a kind of preparation method of APTS modified carbon blacks filling PIM-1 composite membranes, includes the following steps：
It is prepared by S1, PIM-1：By 5,5', 6,6'- tetrahydroxys -3,3,3', 3'- tetramethyl -1,1'- spirals biindolyl, tetrafluoro
Terephthalonitrile, catalyst and the first solvent mixing, be passed through under inert gas conditions, at 140~165 DEG C heating stirring 30~
60min obtains crude product, dissolves the crude product with the second solvent, stirs 5~15min, be filtered, washed, be dried to obtain PIM-
1, wherein, the catalyst includes K2CO3；
It is prepared by S2, modified carbon black：Carbon black nano-particle and 3- aminopropyl triethoxysilanes (APTS) are scattered in third
In solvent, then 50~80min of magnetic agitation is ultrasonically treated 20~40min, obtains modified carbon black solution；
The modified carbon black solution is poured into the PIM-1 solution that mass fraction is 8~12%, is mixed to get casting film by S3
Liquid；
S4, using the cellulose acetate (CA) microfiltration membranes as supporting layer, the casting solution is in the cellulose acetate micro-filtration
Film surface forms active cortex, obtains composite membrane.
The present invention proposes a kind of APTS modified carbon blacks filling PIM-1 composite membranes, is made according to above-mentioned preparation method.
The present invention proposes that one kind isolates and purifies n-butanol method, uses above-mentioned compound membrane separating and purifying butanol solution.
The APTS modified carbon blacks filling PIM-1 composite membranes of the embodiment of the present invention, isolate and purify n-butanol at preparation method
The advantageous effect of method is：
PIM-1 is soluble intrinsic microporous polymer, and the rigidity of itself and the nonplanar structure of molecule can be leaned on to obtain
Micropore compared to other separation membranes, has more excellent selection passability and separative efficiency.Using APTS (3-
Aminopropyltriethoxysilane, 3- aminopropyl triethoxysilane) carbon black is modified, carbon black pellet surface
Hydrophobicity improves, and when introducing PIM matrixes as filler of modified carbon black can improve the hydrophobicity of composite membrane, significantly improve
The infiltration evaporation performance of composite membrane, the composite membrane can have very high n-butanol to detach while high permeating flux is ensured
Ability.
Description of the drawings
It in order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range, for those of ordinary skill in the art, without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the SEM spectrum of the PIM-1 composite membranes of the embodiment of the present invention 2；
Fig. 2 is unmodified carbon black and the infrared spectrogram of APTS modified carbon blacks；
Fig. 3 is the contact angle of PIM-1 composite membranes and the relational graph of modified carbon black additive amount；
Fig. 4 is the degree of swelling of PIM-1 composite membranes and the relational graph of carbon black additive amount；
Fig. 5 is influence figure of the modified carbon black additive amount to PIM-1 composite membrane infiltration evaporation performances；
Fig. 6 is influence figure of the operation temperature to separating property；
Fig. 7 is influence figure of the feed concentration to separating property.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
PIM-1 composite membranes are filled to the APTS modified carbon blacks of the embodiment of the present invention below, preparation method, are isolated and purified just
Butanol method is specifically described.
The preparation method of a kind of APTS modified carbon blacks filling PIM-1 composite membranes provided in an embodiment of the present invention, including following
Step：
It is prepared by S1, PIM-1：By 5,5', 6,6'- tetrahydroxys -3,3,3', 3'- tetramethyl -1,1'- spirals biindolyl, tetrafluoro
Terephthalonitrile, catalyst and the first solvent mixing, be passed through under inert gas conditions, at 140~165 DEG C heating stirring 30~
60min obtains crude product, dissolves crude product with the second solvent, stirs 5~15min, be filtered, washed, be dried to obtain PIM-1,
In, catalyst includes K2CO3。
It is prepared by S2, modified carbon black：Carbon black and 3- aminopropyl triethoxysilanes are scattered in third solvent, magnetic agitation
Then 50~80min is ultrasonically treated 20~40min, obtains modified carbon black solution.
Modified carbon black solution is poured into the PIM-1 solution that mass fraction is 8~12%, is mixed to get casting solution by S3.
S4, using cellulose acetate microfiltration membranes as supporting layer, casting solution forms active skin in cellulose acetate micro-filtration film surface
Layer, obtains composite membrane.
Further, in preferred embodiments of the present invention, in step S1,5,5', 6,6'- tetrahydroxys -3,3,3', 3'-
The mass ratio of tetramethyl -1,1'- spirals biindolyl, tetrafluoro terephthalonitrile and catalyst is 2~2.5：1.5~2：1.In the ratio
Lower obtained PIM-1 matrixes, have better gas permeability and selectivity, and stability is good, and solvable are easy to form a film.With commonly using
Membrane material, such as PVDF compares, and permeates advantage with higher gas, can efficiently separate n-butanol molecule.
Further, it is 1 that catalyst, which is mass ratio,:0.1~0.3 K2CO3And Nd2O3, in catalyst K2CO3Middle addition is few
The rare earth oxide of amount, can effectively facilitate the synthesis of polymer, and molecular weight higher obtains the microporous polymer of higher performance.
Further, in preferred embodiments of the present invention, in PIM-1 composite membranes, the mass fraction of modified carbon black is 0.1
~8%.It is further preferable that the mass fraction of modified carbon black is 4~6%.Modified carbon black has hydrophobic structure, and hydrophobicity prevents
The cohesion of capillary, the n-butanol absorption property of filling-modified composite membrane are good.With the increase of modified carbon black content,
The permeation flux of PIM-1 composite membranes significantly increases, and the separation factor of film significantly increases.But the too high levels of modified carbon black, then
It can lead to the decline of separation factor.
Further, in preferred embodiments of the present invention, the first solvent is that volume ratio is 1:2~3 toluene and N, N-
Dimethylacetylamide.The solvent is more advantageous to the progress of the polycondensation reaction of polymer.Further, in PIM-1 preparation process,
It is passed through under inert gas conditions, is stirred to react using heating stage by stage, be more advantageous to improving the performance of PIM-1 matrixes, such as first
The heating stirring 10min at 140 DEG C, then the heating stirring 40min at 160 DEG C, obtains crude product.
Further, in preferred embodiments of the present invention, the second solvent is chloroform and the mixture of methanol.Use chlorine
Imitative/carbinol mixture dissolving crude product, is obtained by filtration precipitation, solvent and salt in precipitated product is then washed with deionized water,
So as to purified product.Preferably, washed product dry 12h at 100 DEG C obtains PIM-1.
Further, in preferred embodiments of the present invention, third solvent is in chloroform, dichloromethane, tetrachloromethane
It is one or more.
Further, in step S2, the mass ratio of carbon black and APTS are 1~1.2:1, further, mass ratio 1:1.
Under the ratio, effectively carbon black can be modified, obtain the preferable modified carbon black nano-particle of hydrophobic performance.
Further, in step S3, weigh a certain amount of PIM-1, add in suitable solvent, obtain mass fraction for 8~
In 12% PIM-1 solution.Solvent in PIM-1 solution is preferably one kind or more in chloroform, dichloromethane, tetrachloromethane
Kind.Above-mentioned solvent can excellent dissolution PIM-1, convenient for the preparation of follow-up composite membrane and the dispersion of modified carbon black particle.
Further, in preferred embodiments of the present invention, cellulose acetate microfiltration membranes (CA microfiltration membranes) are being located in advance in advance
It manages and 2~3h is impregnated in liquid, pretreatment fluid is water or the alkaline aqueous solution of dopamine.By basement membrane, i.e. CA microfiltration membranes, handling in advance
It is impregnated in liquid, fluid molecule is enabled to occupy the space at basement membrane fenestra and the basement membrane back side so that casting solution is not penetrated into hole
In.Further, when treatment fluid is the alkaline aqueous solution of dopamine, under aqueous basic conditions oxygen can occur for dopamine
Change-auto polymerization reaction, forms the poly-dopamine functional skin layer that strength attaches to substrate surface.Poly-dopamine functional skin layer has excellent
On the one hand different surface-active and Adhering capacity enable to active cortex to combine closely on supporting layer, enhanced products performance.
On the other hand, with the silicone hydroxyl on modified carbon black surface chemical bonded refractory can occur for the amino of poly-dopamine functional skin layer and hydroxyl
It closes, forms secondary function, effectively increase the vaporization permeance property of composite membrane.Further, in alkaline aqueous solution, dopamine
A concentration of 0.7~1g/L, pH values be 8~8.5, suitable poly-dopamine functional skin layer can be formed.
Further, in preferred embodiments of the present invention, composite membrane also passes through post-processing step：Composite membrane is 70~90
It is 2~4 days dry at DEG C.
A kind of APTS modified carbon blacks filling PIM-1 composite membranes provided in an embodiment of the present invention, according to above-mentioned preparation method
It is made.
One kind provided in an embodiment of the present invention isolates and purifies n-butanol method, uses the above-mentioned positive fourth of compound membrane separating and purifying
Alcoholic solution.The feed concentration and operation temperature of butanol solution play the infiltration evaporation performance of PIM composite membranes in crucial work
With, it is preferable that during using compound membrane separating and purifying butanol solution, operation temperature is 20~50 DEG C, feed concentration for 5~
25%.
Embodiment 1
A kind of APTS modified carbon blacks filling PIM-1 composite membranes provided in this embodiment, are made according to following methods：
(1) pretreatment of supporting layer：CA microfiltration membranes are placed into 2h in deionized water using preceding.
(2) preparation of soluble intrinsic microporous polymer (PIM-1)：8.3g K2CO3, 6.8g 5,5', 6,6'- tetrahydroxy-
3,3,3', 3'- tetramethyl -1,1'- spirals biindolyl, 4g tetrafluoros terephthalonitrile, the toluene of 15mL and the N of 30mL, N- dimethyl
Acetamide is added in 500mL there-necked flasks.The heating stirring at 155 DEG C leads to nitrogen gas stirring.Crude product is collected after 40min.Using
Chloroform/methanol mixture dissolves crude product, stirs 10min, precipitation is obtained by filtration, is washed away in precipitated product using deionized water
Solvent and salt.Then product is placed into 12h in 100 DEG C of vacuum drying chambers, obtains PIM-1 final products.
(3) preparation of PIM-1 solution：A certain amount of PIM-1 is accurately weighed with assay balance, is placed in the beaker of dried and clean
In I, suitable solvent chloroform is added in, obtains the PIM-1 solution that mass fraction is 10%.It is placed on magnetic force on magnetic stirring apparatus
Stir 12h.
(4) preparation of modified carbon black nano-particle：Carbon black nano-particle is placed in 100 DEG C of vacuum drying chambers first,
It is taken out after 48h drying moisture.The carbon black nano-particle of certain mass is taken, then sequentially adds APTS and solvent chloroform, will be mixed
Solution is put on magnetic stirring apparatus after stirring 1h, and then sonic oscillation 30min obtains modified carbon black solution.
(5) preparation of casting solution：Suitable modified carbon black solution is poured into beaker I for 2% by the additive amount of modified carbon black
In, magnetic agitation 1h, standing and defoaming 30min, the uniform mixed liquor of gained is casting solution.
(6) compound film preparation：While casting solution is prepared, CA microfiltration membranes from water are taken out, are tiled on a glass,
The water of upper surface is dried with filter paper, is then fixed on a glass with adhesive tape, glass plate is placed on knifing machine.It will prepare
Good casting solution is poured in CA microfiltration membranes, makes casting solution rapid uniformly expansion in membrane surface, it is uniform to form a layer thickness
Active cortex.
(7) it post-processes：It is complete that substrate and the composite membrane prepared are put into 3 days high-temperature process, solvent in 80 DEG C of drying boxes
It takes out after volatilization, is cleaned using deionized water, gained composite membrane is final products.
PIM-1 composite membranes made from the present embodiment measure infiltration evaporation performance in 40 DEG C of 5% n-butanol aqueous solution, ooze
Saturating flux is 517gm-2h-1, separation factor 12.4.
Embodiment 2
A kind of APTS modified carbon blacks filling PIM-1 composite membranes provided in this embodiment, exist with the difference of embodiment 1
In the additive amount of modified carbon black is 4%.
5% butanol determination of aqueous solution infiltration evaporation performance of the PIM-1 composite membranes made from the present embodiment at 40 DEG C, infiltration
Flux is 566gm-2h-1, separation factor 13.9.
Embodiment 3
A kind of APTS modified carbon blacks filling PIM-1 composite membranes provided in this embodiment, exist with the difference of embodiment 1
In the additive amount of modified carbon black is 6%.
PIM-1 composite membranes made from the present embodiment measure infiltration evaporation performance in 40 DEG C of 5% n-butanol aqueous solution, ooze
Saturating flux is 640gm-2h-1, separation factor 12.6.
Embodiment 4
A kind of APTS modified carbon blacks filling PIM-1 composite membranes provided in this embodiment, exist with the difference of embodiment 2
In the pretreatment of supporting layer：2h is reacted using preceding CA microfiltration membranes are placed in the alkaline aqueous solution that dopamine concentration is 1g/L.
PIM-1 composite membranes made from the present embodiment measure infiltration evaporation performance in 40 DEG C of 5% n-butanol aqueous solution, ooze
Saturating flux is 572gm-2h-1, separation factor 14.8.
Comparative example 1
This comparative example provides a kind of PIM-1 films, and the difference lies in PIM-1 base materials with embodiment 1 for preparation method
In, the additive amount of modified carbon black is 0.
PIM-1 films made from this comparative example measure infiltration evaporation performance in 40 DEG C of 5% n-butanol aqueous solution, and infiltration is logical
It measures as 548gm-2h-1, separation factor 6.4.
Comparative example 2
This comparative example provides a kind of PDMS composite membranes, is made according to following methods：
(1) pretreatment of supporting layer：CA microfiltration membranes are placed into 2h in deionized water using preceding.
(2) preparation of PDMS solution：A certain amount of PDMS is accurately weighed with assay balance, is placed in the beaker I of dried and clean
In, suitable solvent hexane is added in, obtains the PDMS solution that mass fraction is 10%.It is placed on magnetic force on magnetic stirring apparatus
Stir 12h.
(3) preparation of modified carbon black nano-particle：Carbon black nanometer is placed in 100 DEG C of vacuum drying chambers first, 48h dries
It is taken out after solid carbon dioxide point.The carbon black nano-particle of certain mass is taken, APTS and solvent chloroform is then sequentially added, mixed solution is put
After stirring 1h on to magnetic stirring apparatus, then sonic oscillation 30min obtains modified carbon black solution.
(4) preparation of casting solution：Suitable modified carbon black solution is poured into beaker I for 4% by the additive amount of modified carbon black
In, magnetic agitation 1h, standing and defoaming 30min, the uniform mixed liquor of gained is casting solution.
(5) compound film preparation：While casting solution is prepared, CA microfiltration membranes from water are taken out, are tiled on a glass,
The water of upper surface is dried with filter paper, is then fixed on a glass with adhesive tape, glass plate is placed on knifing machine.It will prepare
Good casting solution is poured in CA microfiltration membranes, makes casting solution rapid uniformly expansion in membrane surface, it is uniform to form a layer thickness
Active cortex.
(6) it post-processes：It is complete that substrate and the composite membrane prepared are put into 3 days high-temperature process, solvent in 80 DEG C of drying boxes
It takes out after volatilization, is cleaned using deionized water, gained composite membrane is final products.
PDMS composite membranes made from this comparative example measure infiltration evaporation performance in 40 DEG C of 5% n-butanol aqueous solution, ooze
Saturating flux is 323gm-2h-1, separation factor 7.3.
The SEM spectrum of PIM-1 composite membranes provided as shown in Figure 1 for the embodiment of the present invention 2, it will be seen from figure 1 that intact
Sunken dense composite film is successfully prepared.And in PIM-1 matrixes, show that agglomeration does not occur for modified carbon black, add
Modified carbon black does not have an impact the arrangement of PIM-1 strands.
It is illustrated in figure 2 the infrared spectrogram of carbon black nano-particle.1 infrared spectrogram for unmodified carbon black in Fig. 2,2
Infrared spectrogram for modified carbon black.Modified carbon black is in 2930cm-1(CH2Stretch) and 1470cm-1(CH2Bending) show silicon
The characteristic absorption peak and APTS of alkane coupling agent are in 1720cm-1The characteristic peak of (C=O stretches).In addition, the feature of modified carbon black
The position and intensity of peak and unmodified carbon black are changed, and show to be chemically reacted between APTS and nano carbon black.
It is illustrated in figure 3 the hydrophobicity using water contact angle detection PIM-1 composite membranes.With the increasing of modified carbon black content
Add, film surface contact angle increases, this shows that the addition of modified carbon black improves the hydrophobicity of composite membrane.In the table of Modified Activated Carbon black film
Face, the value of water contact angle are more than the value of unmodified membrane.The value of water contact angle increases with the increase of content of carbon black in film.It is former
Because being that APTS alkane makes the water-wetted surface of carbon black pellet become hydrophobicity.Therefore, it is modified when filler introduces PIM-1 matrixes
The surface hydrophobic of film is effectively improved.
As shown in figure 4, have studied influence of the modified carbon black to PIM-1 composite membrane swelling resistances using equilibrium swelling experiments.From
Fig. 4 can be seen that increasing with modified carbon black content, and the degrees of expansion of PIM-1 composite membranes continuously decreases, it was confirmed that compound
The solvent adsorption ability of film continuously decreases.Main cause is that the addition of modified carbon black is that gap inside composite membrane is reduced, so as to
Improve the anti-Swelling Capacity of composite membrane.As can be seen from the figure the swelling resistance of PIM-1 composite membranes is higher than pure PIM-1 films,
The increase of the anti-Swelling Capacity of PIM-1 composite membranes is caused by the raising of composite membrane interior hydrophobicity and internal voids are reduced.
As shown in figure 5, the infiltration evaporation performance of PIM-1 composite membranes is tested in 40 DEG C of 5wt% butanol solutions.Fig. 5
In, 1 is the variation tendency line of separation factor, and 2 be the variation tendency line of permeation flux.With the increase of modified carbon black content,
The permeation flux of PIM-1 composite membranes significantly increases, and the separation factor of film significantly increases.The increase of separation factor is due to Modified Activated Carbon
Black addition.The hydrophobicity raising of composite membrane is the increased key factor of separation factor.Its immanent cause is that modified carbon black has
Hydrophobic structure, the hydrophobicity of modified carbon black prevent the effect of capillary condensation.Therefore, the fourth of the composite membrane of filling-modified carbon black
Alcohol absorption property is good, and diffusion selectivity plays key effect in solution diffusion mechanism.Butanol molecules, can due to its flexible structure
To pass through composite membrane.Chemical potential gradient is the power that hydrone is made to pass through composite membrane.Therefore, hydrophobic transport path is to butanol molecules
Low friction and lower resistance the reason of being the high permeating flux of butanol.Generally speaking, the volume of butanol molecules is bigger causes to ooze
Saturating rate is relatively low, but because hydrophobic permeation pathway makes the permeability of butanol molecules in composite membrane higher.And hydrone must be multiple
It closes and spirals in film, then produced by the hydrophobic raising of film with more highly selective PIM-1 composite membranes.Fig. 5 is shown
Influence of the modified carbon black content to separation factor.First, separation factor increases with the increase of modified carbon black content, then subtracts
It is small.Suitable modified carbon black particle damage segment it is regularly arranged, increase free volume, still, more modified carbon blacks
Particle can lead to the defects of composite membrane.Seek the balance between above two mechanism, be 4% so as to obtain modified carbon black additive amount
When, best results.
As shown in fig. 6, the infiltration evaporation performance that operation temperature influences PIM-1 composite membranes plays key effect.Therefore, it inquires into
Its influence to infiltration evaporation performance is of great significance.Operation temperature is studied in the n-butanol aqueous solution of 5wt% to PIM-
The influence of 1 compound membrane separating property.In Fig. 6,1 is the variation tendency line of separation factor, and 2 be the variation tendency line of permeation flux.
With the increase of operation temperature, permeation flux significantly improves.However, with the raising of operation temperature, butanol flux is in water flux
Reduce while increase.Temperature improves the chemical potential of upstream portion fourth alcohol and water, leads to the chemical potential difference of upstream and downstream
Increase.And the raising of temperature improves the activity of PIM-1 molecules, so as to increase free volume.With the raising of operation temperature,
The diffusion rate of butanol and hydrone increases.However, butanol molecules are bigger than hydrone, water diffusion rate is increased above butanol
Diffusion rate, so as to improve selectivity.
As shown in fig. 7, PIM-1 feed concentrations are studied in 40 DEG C of 5% butanol aqueous solution to compound membrane separating property
It influences.From Fig. 7,1 is the variation tendency line of separation factor, and 2 be the variation tendency line of permeation flux.With butanol concentration
Increase, total flux significantly increases, and separation factor is gradually reduced.The diffusion of water and butanol molecules is by plastication and the shadow of partial pressure
It rings.On the one hand, the driving force of butanol diffusion is as the partial pressure of butanol increases and increases.With the increase of butanol concentration, increasingly
More butanol molecules are dissolved in PIM-1 composite membranes, so as to increase the degree of swelling of composite membrane, so as to improve free volume,
Lead to the flux of water and butanol all to increase.Excessive compound membrane swelling, leads to permeation pathway caused by excessively high butanol concentration meeting
Hydrophily increases, and shows as the flux increase of water, and the flux of butanol is then reduced as the increase of feed concentration first increases, from
And lead to the reduction of separation factor.
Embodiments described above is part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of APTS modified carbon blacks filling PIM-1 composite membranes, which is characterized in that include the following steps：
It is prepared by S1, PIM-1：By 5,5', 6,6'- tetrahydroxys -3,3,3', 3'- tetramethyl -1,1'- spirals biindolyl, tetrafluoro are to benzene
Dintrile, catalyst and the mixing of the first solvent, are passed through under inert gas conditions, 30~60min of heating stirring at 140~165 DEG C,
Crude product is obtained, the crude product is dissolved with the second solvent, stirs 5~15min, be filtered, washed, be dried to obtain PIM-1,
In, the catalyst includes K2CO3；
It is prepared by S2, modified carbon black：Carbon black nano-particle and 3- aminopropyl triethoxysilanes are scattered in third solvent, magnetic force
50~80min is stirred, 20~40min is then ultrasonically treated, obtains modified carbon black solution；
The modified carbon black solution is poured into the PIM-1 solution that mass fraction is 8~12%, is mixed to get casting solution by S3；
S4, using cellulose acetate microfiltration membranes as supporting layer, the casting solution forms work in the cellulose acetate micro-filtration film surface
Property cortex, obtains composite membrane.
2. preparation method according to claim 1, which is characterized in that in step S1, described 5,5', 6,6'- tetrahydroxy -3,
The mass ratio of 3,3', 3'- tetramethyl -1,1'- spirals biindolyl, the tetrafluoro terephthalonitrile and the catalyst is 2~2.5：
1.5~2：1.
3. preparation method according to claim 1, which is characterized in that in the composite membrane, the quality of the modified carbon black
Score is 0.1~8%.
4. preparation method according to claim 1, which is characterized in that it is 1 that first solvent, which is volume ratio,:2~3 first
Benzene and DMAC N,N' dimethyl acetamide.
5. preparation method according to claim 1, which is characterized in that mixing of second solvent for chloroform and methanol
Object.
6. preparation method according to claim 1, which is characterized in that the third solvent is selected from chloroform, dichloromethane, four
It is one or more in chloromethanes.
7. preparation method according to claim 1, which is characterized in that the cellulose acetate microfiltration membranes are pre-processing in advance
2~3h is impregnated in liquid, the pretreatment fluid is water or the alkaline aqueous solution of dopamine.
8. preparation method according to claim 1, which is characterized in that the composite membrane also passes through post-processing step：It is described
Composite membrane is 2~4 days dry at 70~90 DEG C.
9. a kind of APTS modified carbon blacks fill PIM-1 composite membranes, which is characterized in that according to claim 1~8 any one
Preparation method be made.
10. one kind isolates and purifies n-butanol method, which is characterized in that is filled out using APTS modified carbon blacks as claimed in claim 9
Fill the compound membrane separating and purifying butanol solutions of PIM-1.
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