CN109012241A - A kind of compound forward osmosis membrane and preparation method thereof with separation function - Google Patents
A kind of compound forward osmosis membrane and preparation method thereof with separation function Download PDFInfo
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- CN109012241A CN109012241A CN201811068577.0A CN201811068577A CN109012241A CN 109012241 A CN109012241 A CN 109012241A CN 201811068577 A CN201811068577 A CN 201811068577A CN 109012241 A CN109012241 A CN 109012241A
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D71/26—Polyalkenes
Abstract
A kind of forward osmosis membrane and preparation method thereof with separation function, by preparing the extraordinary forward osmosis membrane with a multivalence stalling characteristic in polymer-based film, it may be implemented to draw a multivalent ion in liquid while increasing forward osmosis membrane flux to be separated, allow monovalent ion to penetrate film and enters material liquid, and multivalent ion cannot pass through, this special type forward osmosis membrane is concentrated in strong brine has special application value from different salt ion ratios in change strong brine.Extraordinary forward osmosis membrane of the invention, not only having the function of concentrating function also has salt component ratio in adjusting water, and with the propulsion of domestic industry wastewater zero discharge project, the extraordinary forward osmosis membrane with a multivalence separation function is with a wide range of applications.
Description
Technical field
The present invention relates to a kind of forward osmosis membrane and preparation method with separation function, this forward osmosis membrane are dense in strong brine
Contracting has special application value from different salt ion ratios in strong brine are changed.
Background technique
Positive infiltration is a kind of novel membrane separation technology.Positive infiltration refers to that water is (or more hypotonic from higher water chemistry gesture
Pressure thoroughly) side region flows to the process of lower water chemistry gesture (or compared with hyperosmosis)-side region by permselectivity membrane.?
Two kinds of solution with different osmotic are placed in two sides with permselectivity membrane respectively, a kind of for compared with Hyposmolality
Material liquid (Feed solution), another kind is, with the driving liquid (Draw solution) compared with hyperosmosis, positive infiltration is just
It is to apply the permeable pressure head of film two sides solution as driving force, just allows the water to spontaneously saturating through selection from material liquid side
The property crossed film reaches driving liquid-side.It is characterized in that not having to impressed pressure is the separation that can reach complex, contamination resistance
By force, it can be operated under normal temperature and pressure, be a kind of separate mode of energy saving, environmental protection, and sustainable development.
Forward osmosis membrane isolation technics had attracted the sight of Many researchers in recent years.Compared with ultrafiltration, reverse osmosis technology,
It is from the advantages of process inherently many uniquenesses, and such as low energy consumption, fouling membrane is light, good separating effect.Due to these features, make
Its application prospect wide in reusing sewage, as sea water desalination, sewage reuse, well-drilling waste water processing, sludge dewatering,
Anaerobic digestion solution concentration, oil and natural gas production waste water recycling etc..
Common forward osmosis membrane structure is in thicker supporting layer (the generally ultrafiltration membrane of phase inversion preparation or positive infiltration
Film) on, a strata amide compacted zone is formed with the method for interfacial polymerization.The forward osmosis membrane of existing preparation is all to try hard to raising water to lead to
Amount reduces the back-mixing flux of salt.Such as Chinese patent CN105597574A " a kind of preparation method of compound forward osmosis membrane ", by quiet
Electrospun prepares nano composite membrane, has preferable rejection flux to be greatly improved salt.In addition Chinese patent
CN106492657A " a kind of preparation method of compound forward osmosis membrane " prepares positive infiltration by the way that nanotube is added in basement membrane
The flux of film, forward osmosis membrane is greatly improved.But in practical applications, it can use the back-mixing amount of salt to change positive infiltration
In the water of permeable membrane two sides the ratio of salt component, reaches special purposes, realizes that concentration is redistributed with salt component by just permeating
There is presently no relevant researchs.
Summary of the invention
The object of the present invention is to provide a kind of compound forward osmosis membrane and preparation method thereof with separation function, by
In polymer-based film preparation have a multivalence separation extraordinary forward osmosis membrane, increase forward osmosis membrane flux while may be implemented by
It draws a multivalent ion in liquid to be separated, allows monovalent ion to penetrate film and enter material liquid, and multivalent ion cannot
Pass through, this special type forward osmosis membrane is concentrated with solute in change strong brine in strong brine than with special application value.
In order to achieve the above object, the present invention adopts the following technical scheme that:
A kind of preparation method of the compound forward osmosis membrane with separation function, comprising the following steps:
(1) it will be contacted in porous support layer and the aqueous phase solution containing two or more reactive amino compounds；
(2) aqueous phase solution of the porous support layer excess surface after water phase infiltrates is removed with rubber rollers；
It (3) will be by step (2) treated porous support layer and the chloride containing two or more acid chloride groups
Close the organic phase solution contact of object；
(4) it is heat-treated, compound forward osmosis membrane is made after washing.
A further improvement of the present invention lies in that porous support layer is the polysulfones that molecular cut off is 3~50,000 in step (1)
One of porous support layer, polyether sulfone porous support layer, sulfonated polyether sulfone porous support layer, polypropylene porous support layer；
The compound containing two or more reactive aminos is aromatic series polyfunctional amine, aliphatic in step (1)
One or more of polyfunctional amine, alicyclic polyfunctional amine, polyhydric alcohol amine.
A further improvement of the present invention lies in that aromatic series polyfunctional amine be m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,
3,5- triaminobenzene, 1,2,4- triaminobenzene, 3,5- diaminobenzoic acid, 2,4 di amino toluene, 2,4- diamino anisole,
One or more of amidol, xylylene diamine；
Aliphatic polyfunctional amine is ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2- aminoethyl) amine, diethylenetriamine
One or more of；
Alicyclic polyfunctional amine is 1,2- diaminocyclohexane, 1,4- diaminocyclohexane, piperazine, 1,3- bipiperidine base third
One or more of alkane, 4- aminomethylpiperazine；
Polyhydric alcohol amine is one or more of ethanol amine, diethanol amine, hexylene glycol amine, diglycolamine.
A further improvement of the present invention lies in that the chloride compounds containing two or more acid chloride groups in step (3)
For one in the multifunctional chloride compounds of aromatic series, the multifunctional chloride compounds of aliphatic, alicyclic multifunctional chloride compounds
Kind is several.
A further improvement of the present invention lies in that the multifunctional chloride compounds of aromatic series are paraphthaloyl chloride, isophthalic diformazan
One or more of acyl chlorides, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride；
The multifunctional chloride compounds of aliphatic be three acyl chlorides of fourth, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides,
One or more of Adipoyl Chloride, sebacoyl chloride, three acyl chlorides of the last of the ten Heavenly stems；
Alicyclic multifunctional chloride compounds are three acyl chlorides of cyclopropane, cyclobutane diacid chloride, four acyl chlorides of cyclobutane, pentamethylene
Diacid chloride, three acyl chlorides of pentamethylene, four acyl chlorides of pentamethylene, hexamethylene diacid chloride, three acyl chlorides of hexamethylene, four acyl chlorides of hexamethylene, tetrahydro
One or more of furans diacid chloride, four acyl chlorides of tetrahydrofuran.
A further improvement of the present invention lies in that containing two or more reactive ammonia in step (1) in aqueous phase solution
The concentration of the compound of base is 1~100g/L；
The concentration of the chloride compounds containing two or more acid chloride groups is 0.5 in organic phase solution in step (3)
~20g/L；
The organic solvent that organic phase solution uses in step (3) for n-hexane, hexamethylene, trifluorotrichloroethane, normal heptane,
One or more of normal octane, toluene, ethylbenzene, IsoparE.
A further improvement of the present invention lies in that the time of contact in step (1) and step (3) is 5~120 seconds；
Heat treatment temperature is 50~120 DEG C in step (4), and heat treatment time is 2~10 minutes.
A further improvement of the present invention lies in that also containing in surfactant, acid absorbent in the aqueous phase solution of step (1)
One or two.
A further improvement of the present invention lies in that surfactant is lauryl sodium sulfate, neopelex, ten
Dialkyl group trimethylammonium bromide, laurel disulfonate acid, Qula lead to one or more of -100, N-Methyl pyrrolidone；
Acid absorbent be one of triethylamine, sodium carbonate, disodium bicarbonate, sodium phosphate, sodium hydroxide, potassium hydroxide or
It is several；
The concentration of surfactant is 0.5~10g/L；The concentration of acid absorbent is 1~20g/L.
A kind of compound forward osmosis membrane with separation function, the forward osmosis membrane include polymeric layer and be located at polymeric layer
On function separating layer.
Compared with prior art, the invention has the benefit that the present invention using interfacial polymerization preparation it is special just
Permeable membrane, by regulation two kinds of reaction monomers of interfacial reaction (containing two or more reactive amino compounds with contain
The chloride compounds of two or more acid chloride groups) ratio and synthesis condition, composite film surface pore size may be implemented
Control and composite film surface charge change, enable composite membrane to a multivalent ion have good separating effect, simultaneously
It can change composite film surface pattern.Compared to existing common forward osmosis membrane, it is strong to have a high contamination resistance of permeable water flux, simultaneously
Monovalent salt ion can be made through forward osmosis membrane, and divalent and the above salt ion cannot penetrate, positive infiltration prepared by the present invention
While film may be implemented that material liquid is concentrated, salt composition in feed change liquid.There is special answer in processing haline water field
With.In water process zero-emission field for changing salt component ratio and concentration in processing salt water, have broad application prospects.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of compound forward osmosis membrane prepared by the present invention；
Fig. 2 is the working principle diagram of compound forward osmosis membrane of the invention.
Specific embodiment
Invention is further described in detail with reference to embodiments, however, these embodiments are only to provide conduct
Illustrate rather than limits the present invention.
The preparation method of forward osmosis membrane with a multivalence separation function of the invention, comprising the following steps:
(1) porous support layer is impregnated in the aqueous phase solution containing two or more reactive amino compounds；
(2) aqueous phase solution of the porous support layer excess surface after water phase infiltrates is removed with rubber rollers；
It (3) will be by step (2) treated porous support layer in the chloride containing two or more acid chloride groups
Close the organic phase solution dipping of object；
(4) the obtained forward osmosis membrane after being heat-treated, washing；
The porous support layer is the polysulfone porous supporting layer that molecular cut off is 3~50,000, polyether sulfone open support
One of layer, sulfonated polyether sulfone porous support layer, polypropylene porous support layer.
The compound containing two or more reactive aminos is aromatic series polyfunctional amine, aliphatic is multifunctional
At least one of amine, alicyclic polyfunctional amine, polyhydric alcohol amine.
The aromatic series polyfunctional amine is preferably m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triaminobenzene, 1,
2,4- triaminobenzene, 3,5- diaminobenzoic acid, 2,4 di amino toluene, 2,4- diamino anisole, amidol, xyxylene
At least one of diamines；The aliphatic polyfunctional amine is preferably ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2-
Aminoethyl) amine, at least one of diethylenetriamine；The alicyclic polyfunctional amine is preferably 1,2- diaminocyclohexane, 1,
At least one of 4- diaminocyclohexane, piperazine, 1,3- bipiperidine base propane, 4- aminomethylpiperazine；The polyhydric alcohol amine
Preferably at least one of ethanol amine, diethanol amine, hexylene glycol amine, diglycolamine.
These polyfunctional amines can be used a kind, and also two or more kinds may be used.
The chloride compounds containing two or more acid chloride groups are the multifunctional chloride compounds of aromatic series, fat
At least one of the multifunctional chloride compounds of race, alicyclic multifunctional chloride compounds；
The multifunctional chloride compounds of aromatic series are preferably paraphthaloyl chloride, m-phthaloyl chloride, phthalyl
At least one of chlorine, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride；The multifunctional acyl chlorides chemical combination of aliphatic
Object is preferably three acyl chlorides of fourth, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides, Adipoyl Chloride, sebacoyl chloride, last of the ten Heavenly stems trigalloyl
At least one of chlorine；The alicyclic multifunctional chloride compounds are preferably three acyl chlorides of cyclopropane, cyclobutane diacid chloride, ring fourth
Four acyl chlorides of alkane, pentamethylene diacid chloride, three acyl chlorides of pentamethylene, four acyl chlorides of pentamethylene, hexamethylene diacid chloride, three acyl chlorides of hexamethylene, ring
At least one of four acyl chlorides of hexane, tetrahydrofuran diacid chloride, four acyl chlorides of tetrahydrofuran.
These multifunctional acyl chlorides can be used a kind, and also two or more kinds may be used.The functional layer of high rejection in order to obtain,
It is preferable to use the multifunctional acyl chlorides of fragrance.
The organic solvent of the organic phase solution is preferably n-hexane, hexamethylene, trifluorotrichloroethane, normal heptane, just pungent
At least one of alkane, toluene, ethylbenzene, ISOPAR solvent naphtha；
The concentration of compound in the aqueous phase solution containing two or more reactive aminos is 1~100g/L；
The concentration of chloride compounds in the organic phase solution containing two or more acid chloride groups is 0.5~20g/
L；
One or both of surfactant, acid absorbent can also be contained in the aqueous phase solution of step (1)；
The surfactant can be anionic surfactant, cationic surfactant or non-ionic surface active
Agent, such as can choose lauryl sodium sulfate, neopelex, dodecyl trimethyl ammonium bromide, lauric acid sulphur
Sour sodium, Qula lead at least one of -100, N-Methyl pyrrolidone；
The acid absorbent be triethylamine, sodium carbonate, disodium bicarbonate, sodium phosphate, sodium hydroxide, in potassium hydroxide extremely
Few one kind.
The concentration of the surfactant is preferably 0.5~10g/L；The concentration of the acid absorbent is preferably 1~20g/
L。
Above-described dip time is 5~120 seconds.
Heat treatment temperature is 50~120 DEG C in step (4), and heat treatment time is 2~10 minutes.
Forward osmosis membrane prepared by the present invention includes polymeric layer and the function separating layer on polymeric layer.
The performance of the extraordinary compound forward osmosis membrane of positive permeability apparatus test of laboratory scale, using deionized water as material liquid,
Simulating certain zero-emission project mixing concentrated salt solution is to draw liquid, and film activity layer is carried out under the conditions of 25 DEG C of air-conditioning constant temperature towards original
The test of feed liquid (FO) mode.Electronic balance connects computer, and the water drawn in liquid is penetrated into from material liquid every one minute record
Quality, conductivity before and after conductivity meter test experiments.So that it is determined that the back-mixing flux of salt.Water flux and salt back-mixing Flux equation
It is as follows:
Wherein, the weight of computer automatic on-line acquisition electronic balance calculates the weight gain Δ for drawing liquid according to the variation of weight
M, Δ t are runing time, and Am is effective membrane area.Jw water flux unit is Lm-2·h-1。
Wherein, Vt and Ct is the volume of t moment material liquid and the concentration of solute, and V0 and C0 are the volume of 0 moment material liquid
With the concentration of solute, concentration of the solute in material liquid is calculated according to the fitting of the proportional relationship of solute conductivity and concentration.Δt
For runing time, Am is effective membrane area.Js salt back-mixing flux unit is gm-2·h-1。
Compound forward osmosis membrane salt rejection rate prepared by the present invention can be calculated using following formula, salt rejection rate R definition
Are as follows:
Wherein, Cf indicates the concentration of salt in aqueous solution before handling；After Cp expression processing in permeate salt concentration.
Embodiment 1
It the use of molecular cut off is 3~50,000 polyether sulfone porous support membranes (i.e. polyether sulfone porous support layer), front and concentration
It is contacted about 60 seconds for the piperazine aqueous phase solution (i.e. aqueous solution) of 1g/L, the polyether sulfone support membrane after the infiltration of piperazine aqueous phase solution is used
Rubber rollers remove redundant solution.Then this support membrane is contacted with the IsoparE solution for the pyromellitic trimethylsilyl chloride that concentration is 1g/L
60 seconds；Then the aramid layer of formation is dried in air, is placed in 65 DEG C of baking oven and handles 5min, then gone at 25 DEG C
It is rinsed in ionized water, obtains compound forward osmosis membrane, the compound forward osmosis membrane prepared saves in deionized water.
Extraordinary forward osmosis membrane prepared by the present invention is subjected to performance characterization using the above method, drawing liquid is 1mol/LNaCl
And 0.5mol/LNa2SO4Solution, pH value 7.5 use formula (1) that water flux is calculated as 36.24Lm-2·h-1, formula
(2) it is 29.26g/m that salt back-mixing flux, which is calculated,2·h。
The performance of composite membrane is tested by the test method of the separating property of aforementioned extraordinary forward osmosis membrane, resulting survey
Test result is listed in table 1.
Embodiment 2
The preparation method is the same as that of Example 1 for composite membrane, and piperazine aqueous phase solution is only changed into 10g/L.It is calculated using formula (1)
It is 34.15Lm to water flux-2·h-1, it is 24.34g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
Embodiment 3
The preparation method is the same as that of Example 1 for composite membrane, and piperazine aqueous phase solution is only changed into 50g/L.It is calculated using formula (1)
It is 32.28Lm to water flux-2·h-1, it is 21.32g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
Embodiment 4
The preparation method is the same as that of Example 1 for composite membrane, and piperazine aqueous phase solution is only changed into 100g/L.It is calculated using formula (1)
Obtaining water flux is 31.28Lm-2·h-1, it is 18.27g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
Comparative example 1
Comparative example chooses the business TFC forward osmosis membrane of HTI company, and the forward osmosis membrane of purchase is started the cleaning processing.Before pressing
The test method for stating the separating property of extraordinary forward osmosis membrane tests the performance of composite membrane, and resulting test result is listed in table
1。
1 test result of table
It can be seen that come from the test result of table 1, relative to business TFC forward osmosis membrane, the present invention prepares special positive infiltration
Membrane flux improves, and to a little higher than business TFC forward osmosis membrane of the rejection of sodium sulphate, but the back-mixing flux of sodium chloride is significantly
It improves, illustrates that forward osmosis membrane prepared by the present invention can effectively realize the separation of a multivalent salts, as aqueous phase monomers concentration increases,
Rejection increases, and water flux decline, salt back-mixing flux also declines.
Embodiment 5
Using molecular cut off be 3~50,000 polyether sulfone porous support membranes, front with concentration be 10g/L o-phenylenediamine and
1g/L triethylamine aqueous phase solution contact about 60 seconds, it is infiltrated after polyether sulfone support membrane with rubber rollers remove redundant solution.Then
This support membrane is contacted 60 seconds with the IsoparE solution for the pyromellitic trimethylsilyl chloride that concentration is 0.5g/L；Then by the polyamides of formation
Amine layer is dried in air, is placed in 65 DEG C of baking oven and is handled 5min, is then rinsed in 25 DEG C of deionized water, is obtained compound
Forward osmosis membrane, the compound forward osmosis membrane prepared save in deionized water.
Extraordinary forward osmosis membrane prepared by the present invention is subjected to performance characterization using the above method, drawing liquid is 1mol/LNaCl
And 0.5mol/LNa2SO4Solution, pH value 7.5 use formula (1) that water flux is calculated as 34.24m-2·h-1, formula (2)
It is 28.38g/m that salt back-mixing flux, which is calculated,2·h。
The performance of composite membrane is tested by the test method of the separating property of aforementioned extraordinary forward osmosis membrane, resulting survey
Test result is listed in table 2.
Embodiment 6
Pyromellitic trimethylsilyl chloride solution is only changed into 5g/L with embodiment 5 by compound membrane preparation method.It is counted using formula (1)
It is 32.15Lm that calculation, which obtains water flux,-2·h-1, it is 27.19g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
Embodiment 7
Pyromellitic trimethylsilyl chloride solution is only changed into 10g/L with embodiment 5 by compound membrane preparation method.It is counted using formula (1)
It is 31.28Lm that calculation, which obtains water flux,-2·h-1, it is 24.32g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
Embodiment 8
Pyromellitic trimethylsilyl chloride solution is only changed into 20g/L with embodiment 5 by compound membrane preparation method.It is counted using formula (1)
It is 30.67Lm that calculation, which obtains water flux,-2·h-1, it is 22.27g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
The test structure of embodiment 5-8 is shown in Table 2.
2 test result of table
It can be seen that come from the test result of table 2, as organic phase monomer concentration increases, retention takes the lead in declining after increasing,
Water flux decline, salt back-mixing flux also decline, and as organic phase monomer concentration increases, composite membrane functional layer thickness are caused to increase,
Water flux and salt back-mixing flux reduce, but rejection gradually rises.
Embodiment 9
Using molecular cut off be 3~50,000 polypropylene porous support membranes (i.e. polypropylene porous support layer), front with contain
2,4- diamino anisoles, amidol contact about 50 seconds with the aqueous phase solution of xylylene diamine, wherein 2,4- in aqueous phase solution
The total concentration of diamino anisole, amidol and xylylene diamine is 50g/L, the polyether sulfone support after aqueous phase solution infiltrates
Film removes redundant solution with rubber rollers.Then by this support membrane and the IsoparE solution containing succinyl chloride and penta 3 acyl chlorides
Contact 20 seconds；Wherein, the total concentration of succinyl chloride and penta 3 acyl chlorides is 10g/L in IsoparE solution, then by the poly- of formation
Amide layer is dried in air, is placed in 50 DEG C of baking oven and is handled 3min, is then rinsed, is answered in 25 DEG C of deionized water
Forward osmosis membrane is closed, the compound forward osmosis membrane prepared saves in deionized water.
Extraordinary forward osmosis membrane prepared by the present invention is subjected to performance characterization using the above method, drawing liquid is 1mol/L
NaCl and 0.5mol/L Na2SO4Solution, pH value 7.5 use formula (1) that water flux is calculated as 33.24m-2·h-1, public
It is 31.26g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
The performance of composite membrane is tested by the test method of the separating property of aforementioned extraordinary forward osmosis membrane, resulting survey
Test result is listed in table 3.
Embodiment 10
Treatment temperature is only changed into 70 DEG C with embodiment 9 by compound membrane preparation method.Water is calculated using formula (1)
Flux is 32.15Lm-2·h-1, it is 28.34g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
Embodiment 11
Treatment temperature is only changed into 120 DEG C with embodiment 9 by compound membrane preparation method.Water is calculated using formula (1)
Flux is 33.28Lm-2·h-1, it is 32.32g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
3 test result of table
It can be seen that come from the test result of table 3, as post-processing temperature increases, retention takes the lead in reducing after increasing, and water is logical
Amount and salt back-mixing flux increase after falling before.The excessively high meeting of temperature is so that composite membrane function damage layer, rejection decline, water flux and
Back-mixing flux increases.
Embodiment 12
It the use of molecular cut off is 3~50,000 polyether sulfone porous support membranes, the water in front and the ethanol amine that concentration is 100g/L
Phase solution contacts about 100 seconds, and the polyether sulfone support membrane rubber rollers after aqueous phase solution infiltrates remove redundant solution.Then by this
Support membrane contacts 50 seconds with the organic solution containing cyclobutane diacid chloride, four acyl chlorides of cyclobutane and pentamethylene diacid chloride；Wherein,
The total concentration of cyclobutane diacid chloride, four acyl chlorides of cyclobutane and pentamethylene diacid chloride is 15g/L in organic solution, and organic solution is adopted
Organic solvent is the mixture of ethylbenzene Yu IsoparE solvent naphtha；Then the aramid layer of formation is dried in air, is put
2min is handled in 70 DEG C of baking oven, is then rinsed in 25 DEG C of deionized water, compound forward osmosis membrane is obtained, and what is prepared answers
Forward osmosis membrane is closed to save in deionized water.
Extraordinary forward osmosis membrane prepared by the present invention is subjected to performance characterization using the above method, drawing liquid is 1mol/L
NaCl and 0.5mol/L Na2SO4Solution, pH value 7.5 use formula (1) that water flux is calculated as 33.28m-2·h-1, public
It is 25.39g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
The performance of composite membrane is tested by the test method of the separating property of aforementioned extraordinary forward osmosis membrane, resulting survey
Test result is listed in table 4.
Embodiment 13
The preparation method is the same as that of Example 12 for composite membrane, will only handle the time in baking oven and change into 5min.It is calculated using formula (1)
Obtaining water flux is 31.13Lm-2·h-1, it is 23.92g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
Embodiment 14
The preparation method is the same as that of Example 12 for composite membrane, will only handle the time in baking oven and change into 10min.It is counted using formula (1)
It is 33.35Lm that calculation, which obtains water flux,-2·h-1, it is 26.43g/m that salt back-mixing flux, which is calculated, in formula (2)2·h。
4 test result of table
It can be seen that come from the test result of table 4, as finishing time is elongated, retention takes the lead in reducing after increasing, and water is logical
Amount and salt back-mixing flux increase after falling before.The too long meeting of finishing time is so that composite membrane function damage layer, rejection decline, water
Flux and back-mixing flux increase.
It will be seen from figure 1 that the extraordinary smooth contamination resistance in forward osmosis membrane surface prepared by the present invention is strong.
Figure it is seen that forward osmosis membrane operation logic figure prepared by the present invention, has compared to common forward osmosis membrane
Special application.
Embodiment 15
It the use of molecular cut off is 3~50,000 polyether sulfone porous support membranes, the m-phenylene diamine (MPD) water phase that front is 1g/L with concentration
Solution contacts about 5 seconds, and the polyether sulfone support membrane rubber rollers after the infiltration of piperazine aqueous phase solution remove redundant solution.Then by this
Support membrane contacts 120 seconds with the hexane solution for the biphenyl dimethyl chloride that concentration is 0.5g/L；Then by the aramid layer of formation
Dry in air, be placed in 50 DEG C of baking oven and handle 10min, then rinsed in 25 DEG C of deionized water, obtain it is compound just
Permeable membrane, the compound forward osmosis membrane prepared save in deionized water.
Embodiment 16
It the use of molecular cut off is 3~50,000 polysulfone porous support membranes (i.e. polysulfone porous supporting layer), front is with concentration
The 1 of 20g/L, 3,5- triaminobenzene aqueous phase solutions contact about 20 seconds, and the polyether sulfone support membrane after the infiltration of piperazine aqueous phase solution is used
Rubber rollers remove redundant solution.Then by this support membrane and the cyclohexane solution containing benzene-disulfo-chloride and pyromellitic trimethylsilyl chloride
Contact 100 seconds；Wherein, the total concentration of benzene-disulfo-chloride and pyromellitic trimethylsilyl chloride is 3g/L in cyclohexane solution, then by shape
At aramid layer dry in air, be placed in 70 DEG C of baking oven and handle 8min, then rinsed in 25 DEG C of deionized water,
Compound forward osmosis membrane is obtained, the compound forward osmosis membrane prepared saves in deionized water.
Embodiment 17
It the use of molecular cut off is 3~50,000 sulfonated polyether sulfone porous support membranes (i.e. sulfonated polyether sulfone porous support layer), just
Face contacts about 120 seconds with 3,5- diaminobenzoic acid and 2, the aqueous phase solution of 4- diaminotoluene is contained, wherein in aqueous phase solution
3,5- diaminobenzoic acids and 2, the total concentration of 4- diaminotoluene are 40g/L, the polyether sulfone after the infiltration of piperazine aqueous phase solution
Support membrane removes redundant solution with rubber rollers.Then the trifluorotrichloroethane for three acyl chlorides of fourth for being 8g/L by this support membrane and concentration
Solution contacts 5 seconds；Then the aramid layer of formation is dried in air, is placed in 120 DEG C of baking oven and handles 2min, then exists
It is rinsed in 25 DEG C of deionized water, obtains compound forward osmosis membrane, the compound forward osmosis membrane prepared saves in deionized water.
Embodiment 18
Using molecular cut off be 3~50,000 polypropylene porous support membranes (i.e. polypropylene porous support layer), front with contain
2,4- diamino anisoles, amidol contact about 50 seconds with the aqueous phase solution of xylylene diamine, wherein 2,4- in aqueous phase solution
The total concentration of diamino anisole, amidol and xylylene diamine is 50g/L, the polyether sulfone after the infiltration of piperazine aqueous phase solution
Support membrane removes redundant solution with rubber rollers.Then by this support membrane and the IsoparE containing succinyl chloride and penta 3 acyl chlorides
Solution contacts 20 seconds；Wherein, the total concentration of succinyl chloride and penta 3 acyl chlorides is 10g/L in IsoparE solution, then will be formed
Aramid layer dry in air, be placed in 100 DEG C of baking oven and handle 3min, then rinsed in 25 DEG C of deionized water,
Compound forward osmosis membrane is obtained, the compound forward osmosis membrane prepared saves in deionized water.
Embodiment 19
It the use of molecular cut off is 3~50,000 polyether sulfone porous support membranes, 1, the 2- diamino that front is 60g/L with concentration
The aqueous phase solution of hexamethylene contacts about 100 seconds, and the rubber rollers of the polyether sulfone support membrane after the infiltration of piperazine aqueous phase solution remove more
Remaining solution.Then by this support membrane with contain glutaryl chlorine, oneself three acyl chlorides, three acyl chlorides of Adipoyl Chloride, sebacoyl chloride and the last of the ten Heavenly stems
N-heptane solution contacts 30 seconds；Wherein, glutaryl chlorine in n-heptane solution, oneself three acyl chlorides, Adipoyl Chloride, sebacoyl chloride and last of the ten Heavenly stems
The total concentration of three acyl chlorides is 7g/L, then dries the aramid layer of formation in air, is placed in 80 DEG C of baking oven and handles
Then 5min is rinsed in 25 DEG C of deionized water, obtain compound forward osmosis membrane, and the compound forward osmosis membrane prepared is stored in
In ionized water.
Embodiment 20
Using molecular cut off be 3~50,000 polyether sulfone porous support membranes, front with contain 1,3- bipiperidine base propane and
The aqueous phase solution of 4- aminomethylpiperazine contacts about 70 seconds, wherein 1,3- bipiperidine base propane and 4- amino first in aqueous phase solution
The total concentration of base piperazine is 85g/L, and the polyether sulfone support membrane rubber rollers after the infiltration of piperazine aqueous phase solution remove redundant solution.
Then this support membrane is contacted 70 seconds with the organic solution for three acyl chlorides of cyclopropane that concentration is 20g/L；It is used in organic solution
Organic solvent is the mixture of normal heptane, normal octane and toluene, then dries the aramid layer of formation in air, is placed on 75
DEG C baking oven in handle 7min, then rinsed in 25 DEG C of deionized water, obtain compound forward osmosis membrane, prepare it is compound just
Permeable membrane saves in deionized water.
Embodiment 21
It the use of molecular cut off is 3~50,000 polyether sulfone porous support membranes, the water in front and the ethanol amine that concentration is 100g/L
Phase solution contacts about 100 seconds, and the polyether sulfone support membrane rubber rollers after the infiltration of piperazine aqueous phase solution remove redundant solution.Then
This support membrane is contacted 50 seconds with the organic solution containing cyclobutane diacid chloride, four acyl chlorides of cyclobutane and pentamethylene diacid chloride；
Wherein, the total concentration of cyclobutane diacid chloride, four acyl chlorides of cyclobutane and pentamethylene diacid chloride is 15g/L in organic solution, organic
The organic solvent that solution uses is the mixture of ethylbenzene and IsoparE solvent naphtha；Then in air by the aramid layer of formation
It dries, is placed in 105 DEG C of baking oven and handles 3min, then rinsed in 25 DEG C of deionized water, obtain compound forward osmosis membrane, make
The compound forward osmosis membrane got ready saves in deionized water.
Embodiment 22
Using molecular cut off be 3~50,000 polyether sulfone porous support membranes, front with contain diethanol amine and hexylene glycol amine
Aqueous phase solution contact about 50 seconds, wherein in aqueous phase solution the total concentration of diethanol amine and hexylene glycol amine be 30g/L, through piperazine
Polyether sulfone support membrane after the infiltration of piperazine aqueous phase solution removes redundant solution with rubber rollers.Then this support membrane and pentamethylene will be contained
The contact of IsoparE solution 110 seconds of four acyl chlorides, four acyl chlorides of hexamethylene diacid chloride, three acyl chlorides of hexamethylene and hexamethylene；Wherein,
Four acyl chlorides of pentamethylene in IsoparE solution, four acyl chlorides of hexamethylene diacid chloride, three acyl chlorides of hexamethylene and hexamethylene total concentration be
13g/L；Then the aramid layer of formation is dried in air, is placed in 90 DEG C of baking oven and handles 4min, then at 25 DEG C
It is rinsed in deionized water, obtains compound forward osmosis membrane, the compound forward osmosis membrane prepared saves in deionized water.
Embodiment 23
Using molecular cut off be 3~50,000 polyether sulfone porous support membranes, front with containing diethanol amine, hexylene glycol amine with
And the aqueous phase solution of diglycolamine contacts about 90 seconds, wherein diethanol amine in aqueous phase solution, hexylene glycol amine and diglycolamine
Total concentration is 75g/L, and the polyether sulfone support membrane rubber rollers after the infiltration of piperazine aqueous phase solution remove redundant solution.Then by this
Support membrane contacts 115 seconds with the IsoparE solution containing four acyl chlorides of tetrahydrofuran diacid chloride and tetrahydrofuran；Wherein,
The total concentration of four acyl chlorides of tetrahydrofuran diacid chloride and tetrahydrofuran is 17g/L in IsoparE solution, then by the polyamides of formation
Amine layer is dried in air, is placed in 110 DEG C of baking oven and is handled 3min, is then rinsed, is answered in 25 DEG C of deionized water
Forward osmosis membrane is closed, the compound forward osmosis membrane prepared saves in deionized water.
Embodiment 24
It the use of molecular cut off is 3~50,000 polyether sulfone porous support membranes, front liquid compatible with water contacts about 60 seconds, wherein
Aqueous phase solution is made by the following method: m-phenylene diamine (MPD) being added to the water with surfactant obtained, and in aqueous phase solution
The concentration of m-phenylene diamine (MPD) is 5g/L, and the concentration of surfactant is 0.5g/L in aqueous phase solution, and surfactant is dodecyl
Sodium sulphate；Polyether sulfone support membrane rubber rollers after aqueous phase solution infiltrates remove redundant solution.Then by this support membrane with it is dense
Degree is that the IsoparE solution of the m-phthaloyl chloride of 1g/L contacts 60 seconds；Then the aramid layer of formation is dried in air,
It is placed in 65 DEG C of baking oven and handles 3min, then rinsed in 25 DEG C of deionized water, obtain compound forward osmosis membrane, prepare
Compound forward osmosis membrane saves in deionized water.
Embodiment 25
It the use of molecular cut off is 3~50,000 polyether sulfone porous support membranes, front liquid compatible with water contacts about 60 seconds, wherein
Aqueous phase solution is made by the following method: m-phenylene diamine (MPD) being added to the water with surfactant obtained, and in aqueous phase solution
The concentration of m-phenylene diamine (MPD) is 5g/L, and the concentration of surfactant is 10g/L in aqueous phase solution, and surfactant is lauric acid sulfonic acid
The mixture of sodium and Qula logical -100；Polyether sulfone support membrane rubber rollers after aqueous phase solution infiltrates remove redundant solution.So
This support membrane is contacted 60 seconds with the IsoparE solution for the m-phthaloyl chloride that concentration is 1g/L afterwards；Then by the polyamides of formation
Amine layer is dried in air, is placed in 65 DEG C of baking oven and is handled 3min, is then rinsed in 25 DEG C of deionized water, is obtained compound
Forward osmosis membrane, the compound forward osmosis membrane prepared save in deionized water.
Embodiment 26
It the use of molecular cut off is 3~50,000 polyether sulfone porous support membranes, front liquid compatible with water contacts about 60 seconds, wherein
Aqueous phase solution is made by the following method: m-phenylene diamine (MPD), surfactant and acid absorbent is added to the water obtained, and
The concentration of m-phenylene diamine (MPD) is 5g/L in aqueous phase solution, and the concentration of surfactant is 5g/L in aqueous phase solution, acid absorbent it is dense
Degree is 1g/L, and surfactant is dodecyl trimethyl ammonium bromide, and acid absorbent is triethylamine；After aqueous phase solution infiltrates
Polyether sulfone support membrane removes redundant solution with rubber rollers.Then the m-phthaloyl chloride for being 1g/L by this support membrane and concentration
IsoparE solution contacts 60 seconds；Then the aramid layer of formation is dried in air, is placed in 65 DEG C of baking oven and handles
Then 3min is rinsed in 25 DEG C of deionized water, obtain compound forward osmosis membrane, and the compound forward osmosis membrane prepared is stored in
In ionized water.
Embodiment 27
It the use of molecular cut off is 3~50,000 polyether sulfone porous support membranes, front liquid compatible with water contacts about 60 seconds, wherein
Aqueous phase solution is made by the following method: m-phenylene diamine (MPD), surfactant and acid absorbent is added to the water obtained, and
The concentration of m-phenylene diamine (MPD) is 5g/L in aqueous phase solution, and the concentration of surfactant is 5g/L in aqueous phase solution, acid absorbent it is dense
Degree is 20g/L, and surfactant is dodecyl trimethyl ammonium bromide, and acid absorbent is the mixing of sodium carbonate and disodium bicarbonate
Object；Polyether sulfone support membrane rubber rollers after aqueous phase solution infiltrates remove redundant solution.Then it is with concentration by this support membrane
The IsoparE solution of the m-phthaloyl chloride of 1g/L contacts 60 seconds；Then the aramid layer of formation is dried in air, is placed on
3min is handled in 65 DEG C of baking oven, is then rinsed in 25 DEG C of deionized water, compound forward osmosis membrane is obtained, and what is prepared is compound
Forward osmosis membrane saves in deionized water.
Surfactant in the present invention can also be dodecyl trimethyl ammonium bromide, laurel disulfonate acid, N- methyl
One or more of pyrrolidones；Acid absorbent can also be one of sodium phosphate, sodium hydroxide, potassium hydroxide or several
Kind.
Claims (10)
1. a kind of preparation method of the compound forward osmosis membrane with separation function, which comprises the following steps:
(1) it will be contacted in porous support layer and the aqueous phase solution containing two or more reactive amino compounds；
(2) aqueous phase solution of the porous support layer excess surface after water phase infiltrates is removed with rubber rollers；
It (3) will be by step (2) treated porous support layer and chloride compounds containing two or more acid chloride groups
Organic phase solution contact；
(4) it is heat-treated, compound forward osmosis membrane is made after washing.
2. a kind of preparation method of compound forward osmosis membrane with separation function according to claim 1, which is characterized in that
Porous support layer is the polysulfone porous supporting layer that molecular cut off is 3~50,000, polyether sulfone porous support layer, sulfonation in step (1)
One of polyether sulfone porous support layer, polypropylene porous support layer；
The compound containing two or more reactive aminos is aromatic series polyfunctional amine, the more officials of aliphatic in step (1)
One or more of energy amine, alicyclic polyfunctional amine, polyhydric alcohol amine.
3. a kind of preparation method of compound forward osmosis membrane with separation function according to claim 2, which is characterized in that
Aromatic series polyfunctional amine is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triaminobenzene, 1,2,4- triaminobenzene, 3,5-
One of diaminobenzoic acid, 2,4 di amino toluene, 2,4- diamino anisole, amidol, xylylene diamine are several
Kind；
Aliphatic polyfunctional amine is ethylenediamine, in propane diamine, butanediamine, pentanediamine, three (2- aminoethyl) amine, diethylenetriamine
It is one or more of；
Alicyclic polyfunctional amine be 1,2- diaminocyclohexane, 1,4- diaminocyclohexane, piperazine, 1,3- bipiperidine base propane,
One or more of 4- aminomethylpiperazine；
Polyhydric alcohol amine is one or more of ethanol amine, diethanol amine, hexylene glycol amine, diglycolamine.
4. a kind of preparation method of compound forward osmosis membrane with separation function according to claim 1, which is characterized in that
The chloride compounds containing two or more acid chloride groups are the multifunctional chloride compounds of aromatic series, aliphatic in step (3)
One or more of multifunctional chloride compounds, alicyclic multifunctional chloride compounds.
5. a kind of preparation method of compound forward osmosis membrane with separation function according to claim 4, which is characterized in that
The multifunctional chloride compounds of aromatic series be paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride,
One or more of benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride；
The multifunctional chloride compounds of aliphatic be three acyl chlorides of fourth, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides, oneself two
One or more of acyl chlorides, sebacoyl chloride, three acyl chlorides of the last of the ten Heavenly stems；
Alicyclic multifunctional chloride compounds are three acyl chlorides of cyclopropane, cyclobutane diacid chloride, four acyl chlorides of cyclobutane, two acyl of pentamethylene
Chlorine, three acyl chlorides of pentamethylene, four acyl chlorides of pentamethylene, hexamethylene diacid chloride, three acyl chlorides of hexamethylene, four acyl chlorides of hexamethylene, tetrahydrofuran
One or more of diacid chloride, four acyl chlorides of tetrahydrofuran.
6. a kind of preparation method of compound forward osmosis membrane with separation function according to claim 1, which is characterized in that
The concentration of the compound containing two or more reactive aminos is 1~100g/L in aqueous phase solution in step (1)；
In step (3) in organic phase solution the chloride compounds containing two or more acid chloride groups concentration be 0.5~
20g/L；
The organic solvent that organic phase solution uses in step (3) is n-hexane, hexamethylene, trifluorotrichloroethane, normal heptane, just pungent
One or more of alkane, toluene, ethylbenzene, IsoparE.
7. a kind of preparation method of compound forward osmosis membrane with separation function according to claim 1, which is characterized in that
Time of contact in step (1) and step (3) is 5~120 seconds；
Heat treatment temperature is 50~120 DEG C in step (4), and heat treatment time is 2~10 minutes.
8. a kind of preparation method of compound forward osmosis membrane with separation function according to claim 1, which is characterized in that
Also contain one or both of surfactant, acid absorbent in the aqueous phase solution of step (1).
9. a kind of preparation method of compound forward osmosis membrane with separation function according to claim 8, which is characterized in that
Surfactant is lauryl sodium sulfate, neopelex, dodecyl trimethyl ammonium bromide, lauric acid sulfonic acid
Sodium, Qula lead to one or more of -100, N-Methyl pyrrolidone；
Acid absorbent is one of triethylamine, sodium carbonate, disodium bicarbonate, sodium phosphate, sodium hydroxide, potassium hydroxide or several
Kind；
The concentration of surfactant is 0.5~10g/L；The concentration of acid absorbent is 1~20g/L.
10. a kind of compound forward osmosis membrane with separation function of the preparation of preparation method according to claim 1, which is characterized in that
The forward osmosis membrane includes polymeric layer and the function separating layer on polymeric layer.
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| CN111408281A (en) * | 2019-01-07 | 2020-07-14 | 中国石油化工股份有限公司 | Composite forward osmosis membrane and preparation method thereof |
| CN114307646A (en) * | 2021-12-31 | 2022-04-12 | 北京建筑大学 | Preparation method of high-water-flux composite forward osmosis membrane beneficial to permeation of driving agent |
| CN115245758A (en) * | 2021-04-28 | 2022-10-28 | 中国石油化工股份有限公司 | Composite forward osmosis membrane and preparation method and application thereof |
| WO2023040336A1 (en) * | 2021-09-18 | 2023-03-23 | 宁波大学 | Solvent-resistant forward osmosis composite membrane, preparation method therefor, and application thereof |
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| CN114307646A (en) * | 2021-12-31 | 2022-04-12 | 北京建筑大学 | Preparation method of high-water-flux composite forward osmosis membrane beneficial to permeation of driving agent |
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