CN110394069A - Using the polyamide composite film of inorganic additives preparation, its preparation and application - Google Patents
Using the polyamide composite film of inorganic additives preparation, its preparation and application Download PDFInfo
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- CN110394069A CN110394069A CN201810377650.6A CN201810377650A CN110394069A CN 110394069 A CN110394069 A CN 110394069A CN 201810377650 A CN201810377650 A CN 201810377650A CN 110394069 A CN110394069 A CN 110394069A
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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
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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
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Abstract
The invention belongs to UF membrane fields, more particularly, to a kind of polyamide composite film, preparation method and application prepared using inorganic additives for water process.The composite membrane includes polymeric support layer and polyamide active layer, polyamide active layer is reacted to obtain by the polynary amine aqueous solution containing inorganic additives with polynary solution of acid chloride, during the preparation process, interfacial polymerization occurs for polynary amine aqueous solution and polynary solution of acid chloride containing inorganic additives, this modifies polyamide active layer is prepared, to greatly simplifie filming technology.Composite membrane water flux with higher, lower reversed flux salt, preferable antifouling property.
Description
Technical field
The invention belongs to UF membrane fields, use inorganic additives system for water process more particularly, to a kind of
Standby polyamide composite film, preparation method and application.
Background technique
Polyamide composite film is common a kind of polymer film in membrane separating process, and polyamide composite film is poly- by interface
The method of conjunction is prepared by water phase polyamine or alcohol (phenol) with the mutually polynary acyl chlorides of oil or isocyanates reaction, in porous support layer
Surface forms the ultra-thin active layer with peak to valley asperities pattern of one layer of fine and close several hundred nanometer thickness.Traditional polyamide is compound
Film is a kind of aromatic polyamides structure for the high crosslinking reacted by water phase m-phenylene diamine (MPD) and oily phase pyromellitic trimethylsilyl chloride, this
There are two kinds of free volume holes in aramid layer: skeleton hole (network pore) and aggregation hole (aggregate pore).
The pore radius in usual skeleton hole existsBetween, and the pore radius for assembling hole existsBetween, and the radius of hydrone isThe hydration radius of NaCl isHydrone usually can from skeleton hole and aggregation hole in pass through, NaCl be only possible to from
Aggregation passes through in hole, so, the water flux of film is codetermined by two kinds of holes, and the reversed flux salt (or salt rejection rate) of film by
Assemble hole to determine, the superiority and inferiority of membrane separating property, the size for assembling hole plays conclusive effect.
And the aggregation Kong Wugui (aggregation pore size distribution inhomogenous) that traditional interface polymerization is prepared in aramid layer with
Machine is formed, and aggregation hole pore-size distribution is wider, and pore radius is greater thanPart can be passed freely through for NaCl, cause reversed
Flux salt is larger.In addition, the aramid layer relative hydrophobic of this aromatic structure, and rough surface, water flux is relatively low, and
Pollution tendency with higher, i.e., various pollutants are easily adsorbed on film surface.In addition, current filming technology post-processing is more tired
It is trivial, in addition to needing using heat treatment, often requires to use sodium sulfite and liquor natrii hypochloritis carries out impregnating post-processing etc..Cause
How this, be prepared that a kind of surface is smooth, hydrophily is high in a simple way, and aramid layer thickness is small, free volume
The big and aggregation equally distributed thin-film composite membrane in hole realizes high water flux, low reversed flux salt and more preferably resistance tocrocking
Can, it is to suffer from a problem that at present.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of polyamide film composite membrane and its
Preparation method, the polynary amine aqueous solution by that will contain inorganic additives are reacted with polynary solution of acid chloride, and it is modifies to have obtained this
Polyamide active layer afterwards, to solve, water flux present in traditional polyamide composite film at present is not high enough, reversed salt
The technical problem of flux height, antifouling property difference etc..
To achieve the above object, according to one aspect of the present invention, a kind of polyamide composite film, the composite membrane are provided
Further include polyamide active layer, the polyamide active layer by containing inorganic additives polynary amine aqueous solution and polynary acyl chlorides it is molten
Liquid occurs interfacial reaction and obtains；The inorganic additives cannot occur precipitation reaction with the monomer of the polyamine and generate hydrogen-oxygen
Compound precipitating, and the inorganic additives enter the polyamide active layer during interfacial reaction, play occupy-place
And template action, the inorganic additives be eluted after the polyamide active layer internal in-situ formed cavity structure, the sky
The volume of cavity configuration directly affects the free volume radius size of the polyamide composite film, by adjusting inorganic salts addition
The molecular radius size of agent adjusts the free volume radius of the polyamide active layer, has different free volume radiuses to be formed
The polyamide composite film of size.
Preferably, the polyamine in the polynary amine aqueous solution containing inorganic additives is selected from p-phenylenediamine, isophthalic two
Amine, o-phenylenediamine, to one of cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine or a variety of；The inorganic salts
Additive is one of acid salt, basic salt or neutral salt.
Preferably, the basic salt is selected from NaHCO3、Na2CO3、NH4HCO3、(NH4)2CO3、KHCO3And K2CO3。
Preferably, the acid salt is NaHSO3。
Preferably, the neutral salt is selected from LiCl, NaCl, KCl, NH4Cl、Na2SO4、NaNO3And KNO3。
Preferably, in the polynary amine aqueous solution containing inorganic additives, the mass fraction of the inorganic additives
For 1%-15%, the mass fraction of the polyamine is 1%-5%.
Preferably, the polynary acyl chlorides in the polynary solution of acid chloride is selected from equal four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, to benzene
One of dimethyl chloride, o-phthaloyl chloride and Adipoyl Chloride are a variety of, and the mass-volume concentration of the polynary acyl chlorides is
0.05%-0.75%, the solvent of the polynary solution of acid chloride be selected from one of n-hexane, normal heptane, hexamethylene and toluene or
It is a variety of.
Preferably, polymeric support layer is microfiltration membranes or ultrafiltration membrane, and the material of polymeric support layer is selected from polyacrylonitrile, gathers
Ether sulfone, polysulfones, polyimides, polyamide, polyetherimide, polyamidoimide, cellulose acetate, Triafol T or poly-
Vinylidene.
Other side according to the invention provides a kind of preparation method of polyamide composite film, includes the following steps:
(1) the polynary amine aqueous solution containing inorganic additives is prepared, polymeric support layer is immersed in described containing inorganic salts
The polynary amine aqueous solution of additive takes out after sufficiently impregnating；Wherein in the polynary amine aqueous solution containing inorganic additives
Polyamine be selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, to cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine
One of or it is a variety of；The inorganic additives are one of acid salt, basic salt or neutral salt；It is described to add containing inorganic salts
Add in the polynary amine aqueous solution of agent, the mass fraction of the inorganic additives is 1%-15%, the quality point of the polyamine
Number is 1%-5%；
(2) by a surface of step (1) treated polymeric support layer and polynary solution of acid chloride haptoreaction, gathered
Amide composite membrane.
Preferably, the basic salt is selected from NaHCO3、Na2CO3、NH4HCO3、(NH4)2CO3、KHCO3And K2CO3。
Preferably, the acid salt is NaHSO3。
Preferably, the neutral salt is selected from LiCl, NaCl, KCl, NH4Cl、Na2SO4、NaNO3And KNO3。
Preferably, step (2) the polynary acyl chlorides be selected from equal four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride,
One of o-phthaloyl chloride and Adipoyl Chloride are a variety of, and the mass-volume concentration of the polynary acyl chlorides is 0.05%-
0.5%, the solvent of the polynary solution of acid chloride is selected from the one or more of n-hexane, normal heptane, hexamethylene and toluene.
Preferably, step (2) the catalytic time is 1-10min.
Other side according to the invention provides the application of polyamide composite film described in one kind, is used for UF membrane.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
1, inorganic additives are added directly into polynary amine aqueous solution by the present invention occurs interfacial polymerization with polynary acyl chlorides,
This modifies polyamide active layer is prepared, to greatly simplifie filming technology.
2, have thinner, more hydrophilic and free volume bigger by the way that the composite membrane that inorganic additives are prepared is added
Aramid layer obtains higher water flux.Verified, the water flux of composite membrane can be promoted to 75.6LMH.Simultaneously as inorganic
Being added for salt can obtain the aggregation hole of even aperture distribution with the formation for assembling hole in regular aramid layer, so that reversed salt is logical
Amount is substantially reduced.Verified, reversed flux salt can be down to 0.3gMH.Ratio (the Jv/ of comprehensive water flux and reversed flux salt
Js), ratio may be up to 194.5L/g, that is, representing generation 194.5L water purification only needs consumption 1g NaCl, this is in the world can at present
The peak reached.Since with better hydrophily and more smooth film surface, verified, polyamide prepared by the present invention is multiple
Closing film has good antifouling property for common pollutant sodium alginate, and the water flux reduction after pollution is no more than
25%.
Detailed description of the invention
Fig. 1 is comparative example and embodiment 1-4 composite film surface topography scan electron microscope.
Fig. 2 is comparative example and embodiment 1-4 composite membrane contact angle test result.
Fig. 3 is comparative example and embodiment 1-4 composite membrane forward osmosis performance test water flux result.
Fig. 4 is comparative example and the reversed flux salt result of embodiment 1-4 composite membrane forward osmosis performance test.
Fig. 5 is comparative example and embodiment 1-4 composite membrane forward osmosis performance test water flux/reversed flux salt result.
Fig. 6 is comparative example and embodiment 1-4 composite membrane antipollution test result.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of polyamide composite film, which includes polymeric support layer, further includes that polyamide is living
Property layer, polyamide active layer occurs interfacial reaction by polynary amine aqueous solution and polynary solution of acid chloride containing inorganic additives and obtains
It arrives；Precipitation reaction cannot occur with the monomer of polyamine and generate hydroxide precipitating for inorganic additives；And the inorganic salts add
Agent enters the polyamide active layer during interfacial reaction, and specifically, inorganic additives can be with amine monomers one
It rises and enters organic phase, can be equally wrapped by during interfacial polymerization process forms aramid layer, in polyamide active layer
Play occupy-place and template action, the inorganic additives be eluted after polyamide active layer internal in-situ formed cavity structure,
The free volume of polyamide composite film includes skeleton hole and aggregation hole, and polyamide molecule itself is accounted for there are skeleton hole by inorganic salts
The practical volume for the cavity structure that position is formed is the size for assembling hole in polyamide composite film, therefore formed by inorganic salts occupy-place
Cavity structure directly affects the free volume size of polyamide composite film, by adjusting the molecular radius of the inorganic additives
Size adjusts the free volume radius of the polyamide active layer, to form the polyamide with different free volume radius sizes
Composite membrane.
If prepare it is a kind of for removing the polyamide composite film of sodium chloride in water, as long as requiring the inorganic salts of occupy-place
The free volume radius of the polyamide composite film is not more than the hydration radius of sodium chloride after additive elution；If for taking off
Other metal ions in water removal, such as bivalent metal ion or high-valency metal salt, as long as requiring the inorganic additives of occupy-place
The free volume radius of the polyamide composite film is not more than the correspondingly hydration radius of divalent or high-valency metal salt after elution,
In this way, can according to need the type by adjusting inorganic additives to adjust the free volume radius of polyamide composite film.
Polyamine in polynary amine aqueous solution containing inorganic additives be selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine,
To one of cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine or a variety of；Inorganic additives be acid salt,
One of basic salt or neutral salt.Basic salt can be selected from NaHCO3、Na2CO3、NH4HCO3、(NH4)2CO3、KHCO3And K2CO3；
Acid salt such as NaHSO3；Neutral salt can be selected from LiCl, NaCl, KCl, NH4Cl、Na2SO4、NaNO3And KNO3.Wherein with acid
The compound film properties that salt is prepared are more preferably.In polynary amine aqueous solution containing inorganic additives, the quality of inorganic additives
Score is 1%-15%, and the mass fraction of polyamine is 1%-5%.Polynary acyl chlorides in polynary solution of acid chloride is selected from equal benzene tetramethyl
One of acyl chlorides, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride and Adipoyl Chloride are a variety of, polynary acyl chlorides
Mass-volume concentration (unit are as follows: g/100 milliliters) be 0.05%-0.75%, the solvent of polynary solution of acid chloride be selected from n-hexane,
One of normal heptane, hexamethylene and toluene are a variety of.Polymeric support layer be microfiltration membranes or ultrafiltration membrane, polymeric support layer
Material is selected from polyacrylonitrile, polyether sulfone, polysulfones, polyimides, polyamide, polyetherimide, polyamidoimide acetate fiber
Element, Triafol T or Kynoar.
The preparation method of polyamide composite film provided by the invention, includes the following steps:
(1) the polynary amine aqueous solution containing inorganic additives is prepared, polymeric support layer is immersed in described containing inorganic salts
The polynary amine aqueous solution of additive takes out after sufficiently impregnating；Normally, 1-2min can reach the purpose sufficiently impregnated.Sufficiently
Time needed for impregnating is related to the concentration of polynary amine aqueous solution, and usual 1-10min may make the absorption of polyamine to reach saturation.
Wherein the polyamine in the polynary amine aqueous solution containing inorganic additives be selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine,
To one of cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine or a variety of；The inorganic additives are acid
One of salt, basic salt or neutral salt；In the polynary amine aqueous solution containing inorganic additives, the inorganic additives
Mass fraction be 1%-15%, the mass fraction of the polyamine is 1%-5%；Basic salt is selected from NaHCO3、Na2CO3、
NH4HCO3、(NH4)2CO3、KHCO3And K2CO3；Acid salt is preferably NaHSO3；Neutral salt be preferably selected from LiCl, NaCl, KCl,
NH4Cl、Na2SO4、NaNO3And KNO3.The too low polyamide active layer that will lead to interfacial polymerization formation of polynary amine concentration not enough causes
Close, composite membrane is selectively low, and the too high polyamide active layer that can make to be formed of concentration is too fine and close, and water flux is caused to reduce.It is inorganic
Modified effect is unobvious when the concentration of salt additives is too low, and when concentration is too high, the polyamide active layer of formation is so dense, water flux
Decline.
(2) by a surface of step (1) treated polymeric support layer and polynary solution of acid chloride haptoreaction 1-
10min obtains polyamide composite film.In this step, polynary acyl chlorides and polyamine occur in the upper surface of polymeric support layer
Interface polymerization reaction.Polynary acyl chlorides is selected from equal four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride
With one of Adipoyl Chloride or a variety of, the mass-volume concentration of the polynary acyl chlorides is 0.05%-0.5%, the polynary acyl
The solvent of solutions of chlorine is selected from the one or more of n-hexane, normal heptane, hexamethylene and toluene.Polyamine containing inorganic additives
The time that aqueous solution is contacted with polynary solution of acid chloride is 1-10min, and the time of contact is too short, polynary acyl chlorides and polyamine and tertiary amine
The polymerization reaction of additive is incomplete, and the time of contact is too long, then the polyamide active layer for reacting formation is too thick, to reduce multiple
Close the water flux of film.
Polyamide composite film provided by the invention can be used for UF membrane, such as water process, de- including underwater gold category ion
It removes, sewage treatment or saline-water reclamation processing.
In interfacial polymerization process, it is polynary that the acid salt or basic salt that the present invention selects can be used as a kind of catalyst absorption
The byproduct hydrogen chloride that amine and polynary acyl chloride reaction are formed, promotes the progress of interface polymerization reaction, to obtain a kind of height friendship
The aromatic polyamides structure of connection.And chloride inorganic salts, water and gas point that basic salt or acid salt and hcl reaction generate
Son can be formed with the formation of polyamide, they can play the role of occupy-place and template during polyamide formation, be lured
Polyamide is led to grow around them.Obtained from composite membrane after water impregnates, they can be eluted out, form uniform pore diameter point
The aggregation hole of cloth, increases the free volume of aramid layer, and effectively improves the water flux of film.And these rise occupy-place and
The substance of template action, footprint are less than chloride hydrate sodium, to ensure that the high salt rejection rate of film.In in addition,
Although property inorganic salts cannot play the role of catalyst, occupy-place and template action can be played, on the one hand regular polyamide
The formation in aggregation hole in layer, while also can effectively increase the free volume in aramid layer, to effectively promote membrane flux.And
The selection of neutral inorganic molecular size also determines the size in aggregation hole aperture in aramid layer, finally determines the salt of film
Rejection.Furthermore the addition of inorganic salts can also inhibit the growth of aramid layer in polynary amine aqueous solution, obtain thinner more smooth
Polyamide, and film surface hydrophily can be promoted to a certain extent.Improved hydrophily and reduced film surface roughness can be with
Reduce the pollution tendency of film surface.
The following are embodiments:
Comparative example
The polymeric support layer of the composite membrane of comparative example is polysulfones microfiltration membranes.The preparation process of the composite membrane includes following step
(1) the m-phenylene diamine (MPD) aqueous solution that mass fraction is 3.4% is prepared, polysulfones base microfiltration membranes are fully immersed in the isophthalic
It is taken out after 2min in two amine aqueous solutions, catches up with the aqueous solution except the polysulfones base micro-filtration film surface；
(2) hexane solution for preparing the pyromellitic trimethylsilyl chloride that mass/volume score is 0.15%, which is poured on wet
Extra solution is outwelled, is obtained compound after contact 1 minute in one surface of the polysulfones base microfiltration membranes through step (1) processing of profit
Film is stored in pure water.
Embodiment 1
Inorganic additives are NaHCO in embodiment 13.The polymeric support layer of composite membrane is polysulfones microfiltration membranes.This is compound
The preparation process of film includes following step
(1) the m-phenylene diamine (MPD) aqueous solution that mass fraction is 3.4% is prepared, is divided in the m-phenylene diamine (MPD) aqueous solution added with quality
The NaHCO that number is 1%3, polysulfones base microfiltration membranes are fully immersed in the m-phenylene diamine (MPD) aqueous solution after 2min and are taken out, are caught up with except this is poly-
The aqueous solution of sulfuryl micro-filtration film surface；
(2) hexane solution for preparing the pyromellitic trimethylsilyl chloride that mass/volume score is 0.15%, which is poured on wet
The upper surface of the polysulfones base microfiltration membranes through step (1) processing of profit outwells extra solution and obtains composite membrane after contact 1 minute,
It is stored in pure water.
Embodiment 2
With embodiment 1, difference is experimental implementation, in step (1), NaHCO in m-phenylene diamine (MPD) aqueous solution3Quality point
Number is 2%.
Embodiment 3
With embodiment 1, difference is experimental implementation, in step (1), NaHCO in m-phenylene diamine (MPD) aqueous solution3Quality point
Number is 3%.
Embodiment 4
With embodiment 1, difference is experimental implementation, in step (1), NaHCO in m-phenylene diamine (MPD) aqueous solution3Quality point
Number is 4%.
Embodiment 5
With embodiment 1, difference is experimental implementation, and in step (1), 3% mass is added in m-phenylene diamine (MPD) aqueous solution
The Na of score2CO3。
Embodiment 6
With embodiment 1, difference is experimental implementation, and in step (1), 3% mass is added in m-phenylene diamine (MPD) aqueous solution
The NH of score4HCO3。
Embodiment 7
With embodiment 1, difference is experimental implementation, and in step (1), 1% mass is added in m-phenylene diamine (MPD) aqueous solution
The NaCl of score.
Embodiment 8
With embodiment 1, difference is experimental implementation, and in step (1), 3% mass is added in m-phenylene diamine (MPD) aqueous solution
The NaCl of score.
Embodiment 9
With embodiment 1, difference is experimental implementation, and in step (1), 5% mass is added in m-phenylene diamine (MPD) aqueous solution
The NaCl of score.
Embodiment 10
With embodiment 1, difference is experimental implementation, and in step (1), 10% mass is added in m-phenylene diamine (MPD) aqueous solution
The NaCl of score.
Embodiment 11
With embodiment 1, difference is experimental implementation, and in step (1), 3% mass is added in m-phenylene diamine (MPD) aqueous solution
The LiCl of score.
Embodiment 12
With embodiment 1, difference is experimental implementation, and in step (1), 3% mass is added in m-phenylene diamine (MPD) aqueous solution
The KCl of score.
To simplify the description, therefore the preparation parameter of embodiment 13- embodiment 11 is included in table 1, in table unlisted parameter with
Embodiment 1 is identical.
The following are analysis of experimental results
Fig. 1 shows the scanning electron microscope (SEM) photograph of the composite membrane of comparative example and embodiment 1-4 preparation, the composite membrane of comparative example preparation
Show typical foliaceous peak-to-valley pattern, and the composite membrane of embodiment 1-4 preparation shows more smooth film surface, especially
It is embodiment 2-4, their peak-to-valley pattern disappears substantially.In general, film surface is more coarse, pollutant is more easy to attach up.Cause
This, this repressed peak-to-valley pattern of embodiment 2-4, so that its is more difficult contaminated.
Fig. 2 shows the contact angle for the composite membrane that comparative example and embodiment 1-4 are prepared, and composite membrane connects in comparative example
Feeler is 81.9 ± 1.4 °, and in embodiment 1-4, the contact angle of composite membrane is respectively less than the composite membrane in control experiment comparative example
Contact angle.In general, the membrane flux of good hydrophilic property is higher, it is more difficult contaminated.
It is logical with the water flux and reversed salt of forward osmosis test device test comparison example and embodiment the 1-4 composite membrane prepared
Amount, specific experiment condition: drawing liquid is 2M sodium-chloride water solution, and feed liquid is deionized water, and feed liquid and the flow velocity for drawing liquid are
0.3L/min, testing time 1h.Three times, to measuring three times, results are averaged as real for every kind of composite films retest
Test result.
As shown in figure 3, water flux of the composite membrane of comparative example preparation in the case where positive penetration modes and pressure delay penetration modes
Respectively 15.7 ± 0.9LMH and 33.8 ± 2.2LMH, and its water flux of composite membrane modified for embodiment 1-4 is obviously improved, most
It can be promoted to 43.6 ± 3.6LMH and 75.6 ± 3.2LMH greatly.It is modified, the water flux of composite membrane is not only improved, and one
Determine to reduce reversed flux salt in degree.
As shown in figure 4, reversed salt of the composite membrane of comparative example preparation in the case where positive penetration modes and pressure delay penetration modes
Flux is 11.4 ± 1.1gMH and 21.0 ± 2.0gMH, and in embodiment 1-4, the reversed flux salt of composite membrane is substantially reduced,
Especially embodiment 3 and embodiment 4, reversed flux salt can be reduced to 0.21 ± 0.03/0.13 ± 0.04gMH and 0.38 ±
0.07/0.28±0.04gMH.And under identical testing conditions relative to the most of polyamide composite films reported,
Water flux is obviously improved, reversed flux salt sharp fall.
Water flux/reversed flux salt ratio meaning is to consume the water yield of 1g NaCl.As shown in figure 5, prepared by comparative example
Water flux of the composite membrane in the case where positive penetration modes and pressure delay penetration modes/reversed flux salt ratio be 1.39 ± 0.06L/
G and 1.62 ± 0.05L/g, in embodiment 1-4, water flux/reversed flux salt ratio of composite membrane is significantly raised, especially
Embodiment 3 and embodiment 4, inverse ratio value be up to 162.9 ± 12.0/188.1 ± 18.9L/g and 173.4 ± 19.9/194.5 ±
24.3L/g, taller one or two number out of the highest inverse ratio value of the polyamide composite film of this anti-odds ratio existing literature report
Magnitude.
Antifouling property test is carried out with the composite membrane that positive penetration equipment prepares comparative example and embodiment 3.Specific experiment
Condition: using the synthetic wastewater that contains 250mg/L sodium alginate as pollutant feed liquid, using the sodium-chloride water solution of 2M as drawing
Liquid, pollutant feed liquid and the flow velocity for drawing liquid are 0.3L/min, carry out 18 hours continuity Contamination measurements, record is multiple in real time
Close the water flux variation of film during the test.After test, deionized water is used to add the item for being twice flow velocity as feed liquid
Backwash 20min is carried out to film under part, then uses pure water as feed liquid real-time measurement water flux recovery situation.
As shown in fig. 6, water flux sharp fall after the compound fouling membrane of comparative example, and flux recovery rate after backwash
Only 70% or so.The composite membrane of embodiment 3 shows outstanding antifouling property, and after pollution 18 hours, water flux rate of descent is all
Lower than 25%, and after backwash, flux recovery rate is up to 93.1%.
Above-mentioned test is carried out to remaining embodiment, also can get similar result.
By the above test result it is found that the present invention is not necessarily to other modified methods, directly using inorganic additives to polyamides
Amine layer is modified, and a kind of high performance composite membrane has been prepared, has greatly simplified filming technology.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of polyamide composite film, the composite membrane includes polymeric support layer, which is characterized in that the composite membrane further includes
Polyamide active layer, the polyamide active layer are occurred by the polynary amine aqueous solution containing inorganic additives with polynary solution of acid chloride
Interfacial reaction obtains；It is heavy that precipitation reaction generation hydroxide cannot occur with the monomer of the polyamine for the inorganic additives
It forms sediment, and the inorganic additives enter the polyamide active layer during interfacial reaction, play occupy-place and template
Effect, the inorganic additives be eluted after the polyamide active layer internal in-situ formed cavity structure, the cavity structure
Volume directly affect the free volume radius size of the polyamide composite film, by adjusting point of the inorganic additives
Sub- radius size adjusts the free volume radius of the polyamide active layer, has different free volume radius sizes to be formed
Polyamide composite film.
2. polyamide composite film as described in claim 1, which is characterized in that the polyamine containing inorganic additives is water-soluble
Polyamine in liquid be selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, to cyclohexanediamine, hexamethylene diamine, polyethyleneimine and to two
One of piperazine is a variety of；The inorganic additives are one of acid salt, basic salt or neutral salt.
3. polyamide composite film as described in claim 1, which is characterized in that the basic salt is selected from NaHCO3、Na2CO3、
NH4HCO3、(NH4)2CO3、KHCO3And K2CO3；The acid salt is preferably NaHSO3；The neutral salt be preferably selected from LiCl,
NaCl、KCl、NH4Cl、Na2SO4、NaNO3And KNO3。
4. polyamide composite film as described in claim 1, which is characterized in that the polyamine containing inorganic additives is water-soluble
In liquid, the mass fraction of the inorganic additives is 1%-15%, and the mass fraction of the polyamine is 1%-5%.
5. polyamide composite film as described in claim 1, which is characterized in that the polynary acyl chlorides choosing in the polynary solution of acid chloride
From one of equal four formyl chloride of benzene, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride and Adipoyl Chloride or more
Kind, the mass-volume concentration of the polynary acyl chlorides is 0.05%-0.75%, the solvent of the polynary solution of acid chloride be selected from just oneself
One of alkane, normal heptane, hexamethylene and toluene are a variety of.
6. a kind of preparation method of polyamide composite film, which is characterized in that the preparation method includes the following steps:
(1) polymeric support layer is immersed in the polynary amine aqueous solution containing inorganic additives, is taken out after sufficiently impregnating；Its
Described in polyamine in the polynary amine aqueous solution containing inorganic additives be selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, right
One of cyclohexanediamine, hexamethylene diamine, polyethyleneimine and piperazidine are a variety of；The inorganic additives are acid
One of salt, basic salt or neutral salt；In the polynary amine aqueous solution containing inorganic additives, the inorganic additives
Mass fraction be 1%-15%, the mass fraction of the polyamine is 1%-5%；
(2) by a surface of step (1) treated polymeric support layer and polynary solution of acid chloride haptoreaction, polyamide is obtained
Composite membrane.
7. preparation method as claimed in claim 6, which is characterized in that the basic salt is selected from NaHCO3、Na2CO3、NH4HCO3、
(NH4)2CO3、KHCO3And K2CO3；The acid salt is NaHSO3；The neutral salt is selected from LiCl, NaCl, KCl, NH4Cl、
Na2SO4、NaNO3And KNO3。
8. preparation method as claimed in claim 6, which is characterized in that step (2) the polynary acyl chlorides is selected from equal four formyl of benzene
One of chlorine, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride and Adipoyl Chloride are a variety of, the polynary acyl
The mass-volume concentration of chlorine is 0.05%-0.5%, and the solvent of the polynary solution of acid chloride is selected from n-hexane, normal heptane, hexamethylene
It is one or more with toluene.
9. preparation method as claimed in claim 6, which is characterized in that step (2) the catalytic time is 1-
10min。
10. the application of the polyamide composite film as described in claim 1 to 5 any one, which is characterized in that be used for UF membrane.
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