CN113244792B - Composite membrane and preparation method and application thereof - Google Patents

Composite membrane and preparation method and application thereof Download PDF

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CN113244792B
CN113244792B CN202110692253.XA CN202110692253A CN113244792B CN 113244792 B CN113244792 B CN 113244792B CN 202110692253 A CN202110692253 A CN 202110692253A CN 113244792 B CN113244792 B CN 113244792B
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phase solution
polyamide layer
composite membrane
solution
water
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CN113244792A (en
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陈可可
刘文超
谭惠芬
洪勇琦
潘巧明
郑宏林
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Bluestar Hangzhou Membrane Industry Co Ltd
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Bluestar Hangzhou Membrane Industry Co Ltd
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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
    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a composite membrane and a preparation method and application thereof, wherein the preparation method comprises the following steps: providing an aqueous phase solution comprising polyglycerol and a first polyamine and an oil phase solution comprising a polybasic acid halide; sequentially placing the water phase solution and the oil phase solution on the surface of the support membrane and carrying out first heat treatment to generate a first polyamide layer; and then providing a functional solution comprising second polyamine and ionic liquid, placing the functional solution on the surface of the first polyamide layer, and carrying out second heat treatment to generate a second polyamide layer, wherein the second polyamide layer extends from the inside of the first polyamide layer to the surface of the first polyamide layer, and the first polyamide layer and the second polyamide layer form a separation layer, so that the composite membrane is obtained. The composite membrane prepared by the preparation method has extremely high water flux and removal rate of toxic and harmful substances such as viruses and bacteria, and the like, simultaneously keeps high divalent ion removal rate and higher monovalent ion transmittance, and can be better applied to water treatment devices such as water purifiers and the like.

Description

Composite membrane and preparation method and application thereof
Technical Field
The invention relates to the technical field of water treatment, in particular to a composite membrane and a preparation method and application thereof.
Background
Conventional household water purifiers are generally classified into two types: one of the water purifiers contains an activated carbon filter element and a PP cotton filter element, although the water purifier has large water yield, toxic components such as bacteria, viruses and the like in produced water cannot be effectively filtered, and the health of a human body can be influenced; another water purifier contains a reverse osmosis membrane (RO) filter element, but because of the high rejection rate of the reverse osmosis membrane to monovalent ions and divalent ions, trace elements in produced water are too low, and researches show that the too low trace elements are also unfavorable to the health of human bodies.
Disclosure of Invention
In view of the above, there is a need to provide a composite membrane, a method for preparing the same and applications thereof; the composite membrane obtained by the preparation method has extremely high low-pressure water flux and extremely high removal rate of toxic and harmful substances such as viruses and bacteria, and can be better applied to water treatment devices such as water purifiers and the like, and high divalent ion removal rate and high monovalent ion transmittance are kept.
A method of making a composite membrane comprising:
providing an aqueous phase solution and an oil phase solution, wherein the aqueous phase solution comprises polyglycerol and a first polyamine, and the oil phase solution comprises a polybasic acyl halide;
providing a support membrane, sequentially placing the aqueous phase solution and the oil phase solution on the surface of the support membrane, and performing first heat treatment to generate a first polyamide layer on the surface of the support membrane, wherein the first polyamide layer further comprises unreacted polyacyl halide; and
providing a functional solution, wherein the functional solution comprises a second polyamine and an ionic liquid, placing the functional solution on the surface of the first polyamide layer, which is far away from the support membrane, and carrying out second heat treatment to generate a second polyamide layer, wherein the second polyamide layer extends from the inside of the first polyamide layer to the surface of the first polyamide layer, which is far away from the support membrane, and the first polyamide layer and the second polyamide layer form a separation layer, so that a composite membrane is obtained.
In one embodiment, the mass fraction of the polyglycerol in the aqueous solution is from 0.1% to 0.5%.
In one embodiment, the polyglycerols are selected from at least one of diglycerol, triglycerol, pentaglycerol, decaglycerol.
In one embodiment, the mass fraction of the first polyamine in the aqueous phase solution is 0.1% to 1.0%, and the mass fraction of the second polyamine in the functional solution is 0.01% to 1.0%.
In one embodiment, the first polyamine and the second polyamine are independently selected from at least one of piperazine and m-phenylenediamine.
In one embodiment, the ionic liquid is selected from at least one of 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butylpyridyl bromide and 1-butylpyridinium chloride.
In one embodiment, the mass fraction of the polybasic acyl halide in the oil phase solution is 0.05% -0.5%, and the polybasic acyl halide is selected from at least one of aromatic polybasic acyl fluoride, aromatic polybasic acyl chloride, aromatic polybasic acyl bromide, aromatic polybasic acyl iodide, aliphatic polybasic acyl fluoride, aliphatic polybasic acyl chloride, aliphatic polybasic acyl bromide and aliphatic polybasic acyl iodide.
In one embodiment, the aqueous phase solution further comprises an acid scavenger, the mass fraction of the acid scavenger in the aqueous phase solution is 1% -3%, and the acid scavenger is selected from at least one of triethylamine and sodium hydroxide.
In one embodiment, the material of the support membrane is selected from at least one of polysulfone, polypropylene or polyacrylonitrile;
and/or a non-woven fabric layer is further provided and is arranged on the surface, far away from the separation layer, of the support membrane in a laminated mode.
A composite membrane prepared by the method for preparing a composite membrane as described above.
Use of a composite membrane as described above in a water treatment device.
In the preparation method of the composite membrane, when the aqueous phase solution and the oil phase solution are subjected to interfacial polymerization, the first polyamine and the polybasic acyl halide are subjected to a crosslinking reaction to generate the first polyamide, and the generated first polyamide forms the first polyamide layer, but due to the water absorption of the polyglycerol, the hydration layer around the polyglycerol molecules can hydrolyze the functional groups of the polybasic acyl halide in the oil phase, and after the functional groups of the polybasic acyl halide are hydrolyzed, the crosslinking reaction of the polybasic acyl halide and the polyamine is terminated, so that the crosslinking degree of the first polyamide layer is destroyed, pores are formed in the first polyamide layer, and the obtained first polyamide layer is in a loose structure.
Then, when the functional solution containing the second polyamine and the ionic liquid is placed on the surface of the loose first polyamide layer, the ionic liquid and the pore surface of the first polyamide layer can swell the pores due to the electric charge to release the unreacted polyacyl halide in the first polyamide layer, at this time, the second polyamine can react with the released polyacyl halide to generate the second polyamide which extends from the pores to the surface of the first polyamide layer and forms the second polyamide layer, and because the amount of polyacyl halide in the second polymerization process is small, the second polyamide layer does not completely cover the surface of the first polyamide layer but partially covers the surface of the first polyamide layer in the form of dots, tubes, etc., so that the second polyamide layer greatly improves the loose structure of the first polyamide layer, and after the first polyamide layer and the second polyamide layer form a separation layer, the specific surface area of the separation layer is greatly increased. Therefore, the composite membrane obtained by the preparation method has extremely high low-pressure water flux and extremely high removal rate of toxic and harmful substances such as viruses, bacteria and the like, simultaneously keeps high divalent ion removal rate and high monovalent ion transmittance, and can be better applied to water treatment devices such as water purifiers and the like.
In addition, the invention can also regulate and control the appearance of the separating layer through the polymerization degree of the polyglycerol in the aqueous phase solution, so as to flexibly regulate and control the performances of the composite membrane, such as water flux and the like. Meanwhile, the preparation process is simple, additional production line equipment is not required in the whole process, large-scale batch production can be completely realized, and the method has extremely high economic benefit.
Drawings
FIG. 1 is an electron micrograph of a composite film obtained in example 1 of the present invention;
FIG. 2 is an electron micrograph of a composite film obtained in example 2 of the present invention;
FIG. 3 is an electron micrograph of a composite film according to comparative example 1 of the present invention;
FIG. 4 is an electron micrograph of a composite film according to comparative example 2 of the present invention;
FIG. 5 is an electron micrograph of a composite film according to comparative example 3 of the present invention;
FIG. 6 is an electron micrograph of a composite film obtained in comparative example 4 of the present invention.
Detailed Description
The composite film provided by the present invention, its preparation method and application will be further described below.
The preparation method of the composite membrane provided by the invention comprises the following steps:
s1, providing an aqueous phase solution and an oil phase solution, wherein the aqueous phase solution includes polyglycerol and a first polyamine, and the oil phase solution includes a polybasic acyl halide;
s2, providing a support membrane, sequentially placing the aqueous phase solution and the oil phase solution on the surface of the support membrane, and performing a first heat treatment to form a first polyamide layer on the surface of the support membrane, wherein the first polyamide layer further includes unreacted polyacyl halide; and
and S3, providing a functional solution, wherein the functional solution comprises a second polyamine and an ionic liquid, placing the functional solution on the surface, away from the support membrane, of the first polyamide layer, and carrying out second heat treatment to generate a second polyamide layer, wherein the second polyamide layer extends from the inner part of the first polyamide layer to the surface, away from the support membrane, of the first polyamide layer, and the first polyamide layer and the second polyamide layer form a separation layer, so that the composite membrane is obtained.
In step S1, the mass fraction of the polyglycerol in the aqueous solution is 0.1% to 0.5%, preferably 0.15% to 0.4%, in view of economic cost and performance of the composite membrane.
Meanwhile, when polyglycerols having different polymerization degrees are used, separation layers having different morphologies can be obtained, and therefore, in an embodiment, the polyglycerols are selected from at least one of diglycerol, triglycerol, pentaglycerol, and decaglycerol, so that polyglycerols having different polymerization degrees are selected according to a morphology required for the separation layers.
In order to enable the formation of a loose first polyamide layer efficiently, the mass fraction of the first polyamine in the aqueous phase solution is 0.1% to 1.0%, preferably 0.1% to 0.8%. In one embodiment, the first polyamine comprises at least one of an aromatic polyamine or an aliphatic polyamine, further preferably comprises at least one of m-phenylenediamine, piperazine or polyethyleneimine, and more preferably piperazine.
In order to absorb the by-product generated by the cross-linking reaction between the first polyamine and the poly acyl halide, in an embodiment, the aqueous solution further includes an acid scavenger, specifically, the mass fraction of the acid scavenger in the aqueous solution is 1% to 3%, preferably 1.5% to 2.5%, and the acid scavenger is selected from at least one of triethylamine and sodium hydroxide.
It is understood that the solvent of the aqueous solution is water.
In one embodiment, the mass fraction of the polyacyl halide in the oil phase solution is 0.05% to 0.5%, preferably 0.1% to 0.35%. The polybasic acyl halide is at least one selected from aromatic polybasic acyl fluoride, aromatic polybasic acyl chloride, aromatic polybasic acyl bromide, aromatic polybasic acyl iodide, aliphatic polybasic acyl fluoride, aliphatic polybasic acyl chloride, aliphatic polybasic acyl bromide and aliphatic polybasic acyl iodide.
Since the stability of the acid chloride group is relatively high, in an embodiment, the poly-acid halide further preferably includes at least one of an aromatic poly-acid chloride and an aliphatic poly-acid chloride, and particularly, the poly-acid halide preferably includes at least one of trimesoyl chloride and adipoyl chloride.
It is understood that the oil phase solution also includes an isoparaffin solvent.
In step S2, the supporting membrane is made of at least one of polysulfone, polypropylene, or polyacrylonitrile, wherein polysulfone is preferably polysulfone because polysulfone is cheap and easily available, has good mechanical strength, good compression resistance, stable chemical properties, no toxicity, and is resistant to biodegradation.
In order to increase the strength of the composite membrane, in one embodiment, a non-woven fabric layer is further provided, and the non-woven fabric layer is arranged on any surface of the support membrane in a stacking manner, in this case, the aqueous phase solution and the oil phase solution are sequentially arranged on the surface of the support membrane, which is far away from the non-woven fabric layer.
Specifically, the step of sequentially placing the aqueous phase solution and the oil phase solution on the surface of the support membrane and performing a first heat treatment includes: firstly, coating a water phase solution on the surface of a support membrane, standing for a period of time to enable the water phase solution to fill holes in the surface layer of the support membrane, removing the redundant water phase solution and drying the surface of the support membrane by blowing, wherein the holes in the surface layer of the support membrane are still filled with the water phase solution; then coating the oil phase solution on the surface of the blow-dried support membrane, standing for a period of time, and removing the redundant oil phase solution; then, a first heat treatment is carried out, the temperature of the first heat treatment is preferably 50-100 ℃, and the time is preferably 2-10 min.
In this step, when the aqueous phase solution and the oil phase solution are brought into contact with each other, an aqueous-oil interface is formed, and at this time, the first polyamide layer is formed from the first polyamide produced by the crosslinking reaction between the first polyamine and the polybasic acid halide, but due to the water absorption of the polyglycerin, the hydrated layer around the polyglycerin molecule can hydrolyze the functional groups of the polybasic acid halide in the oil phase, and after the functional groups of the polybasic acid halide are hydrolyzed, the crosslinking reaction between the polybasic acid halide and the polyamine is terminated, and the degree of crosslinking of the first polyamide layer is destroyed, and pores are formed in the first polyamide layer, so that the resulting first polyamide layer has a porous structure.
The first polyamide layer also includes unreacted polyacyl halide due to the self-limiting nature of the polymerization reaction. Therefore, in step S3, when the functional solution including the second polyamine and the ionic liquid is placed on the surface of the porous first polyamide layer, the ionic liquid and the pore surface of the first polyamide layer can swell the pores due to charge interaction to release unreacted polyacyl halide in the first polyamide layer. At this time, the second polyamine can react with the released polybasic acid halide to form a second polyamide, which extends from the pores to the surface of the first polyamide layer and constitutes a second polyamide layer. And because the amount of the polybasic acyl halide is less in the secondary polymerization process, the second polyamide layer does not completely cover the surface of the first polyamide layer, but covers the surface of the first polyamide layer in the shapes of points, tubes and the like, so that the loose structure of the first polyamide layer is greatly improved by the second polyamide layer, and meanwhile, the specific surface area of the separation layer is greatly increased after the separation layer is formed by the first polyamide layer and the second polyamide layer.
Therefore, the composite membrane obtained by the preparation method has extremely high water flux and removal rate of toxic and harmful substances such as viruses and bacteria, and simultaneously keeps high divalent ion removal rate and higher monovalent ion permeability.
For better swelling the pores of the first polyamide layer, the ionic liquid is preferably a water-soluble ionic liquid, specifically at least one selected from 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butylpyridinium bromide and 1-butylpyridinium chloride.
In one embodiment, the mass fraction of the second polyamine in the functional solution is 0.01% to 1.0%, and the second polyamine includes at least one of an aromatic polyamine or an aliphatic polyamine, and further preferably includes at least one of m-phenylenediamine, piperazine, or polyethyleneimine, and more preferably piperazine. The second polyamine may be selected from the same or different from the first polyamine.
In one embodiment, the temperature of the second heat treatment is preferably 50 ℃ to 100 ℃ and the time is preferably 2min to 10 min.
Therefore, the preparation process is simple, additional production line equipment is not required to be added in the whole process, large-scale batch production can be completely realized, and the method has extremely high economic benefit.
The invention also provides a composite membrane prepared by the preparation method of the composite membrane, which comprises a support membrane and a separation layer arranged on the surface of the support membrane in a laminated manner, wherein the separation layer comprises a first polyamide layer and a second polyamide layer, and the second polyamide layer extends from the inner part of the first polyamide layer to the surface of the first polyamide layer, which is far away from the support membrane.
It should be noted that the second polyamide layer is a discontinuous layered structure, and covers the surface of the first polyamide layer in the shapes of dots, tubes, etc.
In one embodiment, the composite film further comprises a non-woven fabric layer, and the non-woven fabric layer is arranged on the surface of the support film, which faces away from the separation layer in a laminated manner.
The composite membrane has extremely high water flux and removal rate of toxic and harmful substances such as viruses, bacteria and the like, simultaneously keeps high divalent ion removal rate and higher monovalent ion transmittance, and can be better applied to water treatment devices such as water purifiers and the like.
Therefore, the invention also provides the application of the composite membrane in a water treatment device, wherein the water treatment device comprises a water purifier and the like.
Hereinafter, the composite membrane, the preparation method and the application thereof will be further described by the following specific examples.
In the following examples and comparative examples, the water flux (F) was calculated from the volume of water passing through the composite membrane over time, and the formula was: f = V/(a × T), where V is the volume of water passing through the composite membrane per unit time, a is the effective membrane area, and T is the time.
The retention rate (R) is calculated by the concentration of the concentrated water and the concentration of the permeate, and the calculation formula is as follows: r = (1-C)1/C0) X 100%, wherein C1Is the concentration of concentrated water, C0The concentration of the permeate was used.
Example 1
And uniformly mixing piperazine, triethylamine, decaglycerol and water to obtain an aqueous phase solution for later use, wherein the mass fraction of piperazine in the aqueous phase solution is 0.25%, the mass fraction of triethylamine in the aqueous phase solution is 1.5%, and the mass fraction of decaglycerol in the aqueous phase solution is 0.2%.
Uniformly mixing trimesoyl chloride (TMC) with an isoparaffin solvent (Isopar L) to obtain an oil phase solution for later use, wherein the mass fraction of the trimesoyl chloride in the oil phase solution is 0.15%.
And uniformly mixing piperazine and chlorinated 1-butyl-3-methylimidazolium salt to obtain a functional solution for later use, wherein the mass fraction of piperazine in the functional solution is 0.1%.
Firstly coating the water phase solution on a polysulfone support membrane, standing for 60s, pouring out the redundant water phase solution, and drying the membrane surface by cold air; and coating the oil phase solution on the blow-dried membrane surface, standing for 30s, pouring out the redundant oil phase solution, directly putting the membrane into a 80 ℃ blast drying oven for heat treatment for 2min, and forming a loose first polyamide layer on the polysulfone support membrane. And coating the functional solution on the loose first polyamide layer, standing for 30s, removing the residual functional solution on the surface of the membrane, and then putting the membrane into a 70 ℃ oven for heat treatment for 5min to obtain the composite membrane shown in figure 1. The removal rate of the composite membrane obtained by the embodiment on viruses and bacteria reaches more than 99.9 percent.
In addition, the composite film obtained in this example was subjected to a performance test, and the test objects were: A. 2000ppm sodium chloride concentrated water, B2000 ppm magnesium sulfate concentrated water, C2000 ppm sodium chloride and 2000ppm magnesium sulfate mixed concentrated water, wherein the pH value of the concentrated water is 7.
The test conditions were: the test pressure is 0.5MPa, the concentrate flow is 1.0GPM, and the ambient temperature is 25 ℃.
The results of the test were: when the test object A is taken as inflow water, the retention rate of the composite membrane to sodium chloride is 38.4%, and the water flux is 120 LMH; when the test object B is taken as inflow water, the rejection rate of the composite membrane to magnesium sulfate is 99.1%, and the water flux is 77 LMH; when the test object C is taken as inflow water, the rejection rate of the composite membrane to sodium chloride is 10.2%, the rejection rate to magnesium sulfate is 99.8%, and the water flux is 73 LMH.
Example 2
And uniformly mixing piperazine, triethylamine, pentaglycerol and water to obtain an aqueous phase solution for later use, wherein the mass fraction of piperazine in the aqueous phase solution is 0.35%, the mass fraction of triethylamine in the aqueous phase solution is 1.5%, and the mass fraction of pentaglycerol in the aqueous phase solution is 0.35%.
Uniformly mixing trimesoyl chloride (TMC) with an isoparaffin solvent (Isopar L) to obtain an oil phase solution for later use, wherein the mass fraction of the trimesoyl chloride in the oil phase solution is 0.2%.
And uniformly mixing piperazine and 1-butyl-3-methylimidazolium tetrafluoroborate chloride to obtain a functional solution for later use, wherein the mass fraction of piperazine in the functional solution is 0.15%.
Firstly coating the water phase solution on a polysulfone support membrane, standing for 60s, pouring out the redundant water phase solution, and drying the membrane surface by cold air; and coating the oil phase solution on the blow-dried membrane surface, standing for 30s, pouring out the redundant oil phase solution, directly putting the membrane into a 80 ℃ blast drying oven for heat treatment for 2min, and forming a loose first polyamide layer on the polysulfone support membrane. And coating the functional solution on the loose first polyamide layer, standing for 30s, removing the residual functional solution on the surface of the membrane, and then putting the membrane into a 70 ℃ oven for heat treatment for 5min to obtain the composite membrane shown in figure 2. The removal rate of the composite membrane obtained by the embodiment on viruses and bacteria reaches more than 99.9 percent.
Referring to example 1, the composite membrane obtained in this example was subjected to a performance test, and the test results were: when the test object A is taken as inflow water, the retention rate of the composite membrane to sodium chloride is 41.5%, and the water flux is 135 LMH; when the test object B is taken as inflow water, the rejection rate of the composite membrane to magnesium sulfate is 98.9%, and the water flux is 75 LMH; when the test object C is taken as inflow water, the rejection rate of the composite membrane to sodium chloride is 14.8%, the rejection rate to magnesium sulfate is 99.6%, and the water flux is 71 LMH.
Example 3
And uniformly mixing piperazine, triethylamine, diglycerol and water to obtain an aqueous phase solution for later use, wherein the mass fraction of piperazine in the aqueous phase solution is 0.25%, the mass fraction of triethylamine in the aqueous phase solution is 2.0%, and the mass fraction of diglycerol in the aqueous phase solution is 0.40%.
Uniformly mixing trimesoyl chloride (TMC) with an isoparaffin solvent (Isopar L) to obtain an oil phase solution for later use, wherein the mass fraction of the trimesoyl chloride in the oil phase solution is 0.3%.
And uniformly mixing piperazine and 1-butyl-3-methylimidazolium tetrafluoroborate chloride to obtain a functional solution for later use, wherein the mass fraction of piperazine in the functional solution is 0.10%.
Firstly coating the water phase solution on a polysulfone support membrane, standing for 60s, pouring out the redundant water phase solution, and drying the membrane surface by cold air; and coating the oil phase solution on the blow-dried membrane surface, standing for 30s, pouring out the redundant oil phase solution, directly putting the membrane into a 70 ℃ blast drying oven for heat treatment for 3min, and forming a loose first polyamide layer on the polysulfone support membrane. And coating the functional solution on the loose first polyamide layer, standing for 30s, removing the residual functional solution on the surface of the membrane, and then putting the membrane into a 70 ℃ oven for heat treatment for 5min to obtain the composite membrane. The removal rate of the composite membrane obtained by the embodiment on viruses and bacteria reaches more than 99.9 percent.
Referring to example 1, the composite membrane obtained in this example was subjected to a performance test, and the test results were: when the test object A is taken as inflow water, the retention rate of the composite membrane to sodium chloride is 25.3%, and the water flux is 111 LMH; when the test object B is taken as inflow water, the rejection rate of the composite membrane to magnesium sulfate is 92.1%, and the water flux is 66 LMH; when the test object C is taken as inflow water, the rejection rate of the composite membrane to sodium chloride is 8.8%, the rejection rate to magnesium sulfate is 94.5%, and the water flux is 60 LMH.
Example 4
And uniformly mixing piperazine, triethylamine, triglycerin and water to obtain an aqueous phase solution for later use, wherein the mass fraction of piperazine in the aqueous phase solution is 0.55%, the mass fraction of triethylamine in the aqueous phase solution is 2.0%, and the mass fraction of triglycerin in the aqueous phase solution is 0.4%.
Uniformly mixing trimesoyl chloride (TMC) with an isoparaffin solvent (Isopar L) to obtain an oil phase solution for later use, wherein the mass fraction of the trimesoyl chloride in the oil phase solution is 0.2%.
And uniformly mixing piperazine and 1-butylpyridinium chloride to obtain a functional solution for later use, wherein the mass fraction of piperazine in the functional solution is 0.10%.
Firstly coating the water phase solution on a polysulfone support membrane, standing for 60s, pouring out the redundant water phase solution, and drying the membrane surface by cold air; and coating the oil phase solution on the blow-dried membrane surface, standing for 30s, pouring out the redundant oil phase solution, directly putting the membrane into a 70 ℃ blast drying oven for heat treatment for 3min, and forming a polyamide layer on the polysulfone support membrane to obtain the composite membrane. And coating the functional solution on the loose first polyamide layer, standing for 30s, removing the residual functional solution on the surface of the diaphragm, and then putting the diaphragm into an oven at 80 ℃ for heat treatment for 8min to obtain the composite membrane. The removal rate of the composite membrane obtained by the embodiment on viruses and bacteria reaches more than 99.9 percent.
Referring to example 1, the composite membrane obtained in this example was subjected to a performance test, and the test results were: when the test object A is taken as inflow water, the retention rate of the composite membrane to sodium chloride is 33.6%, and the water flux is 97 LMH; when the test object B is taken as inflow water, the rejection rate of the composite membrane to magnesium sulfate is 94.6%, and the water flux is 56 LMH; when the test object C is taken as inflow water, the rejection rate of the composite membrane to sodium chloride is 21.7%, the rejection rate to magnesium sulfate is 97.2%, and the water flux is 48 LMH.
Comparative example 1
And uniformly mixing piperazine, triethylamine, pentaglycerol and water to obtain an aqueous phase solution for later use, wherein the mass fraction of piperazine in the aqueous phase solution is 0.6%, the mass fraction of triethylamine in the aqueous phase solution is 2.5%, and the mass fraction of pentaglycerol in the aqueous phase solution is 0.45%.
Uniformly mixing trimesoyl chloride (TMC) with an isoparaffin solvent (Isopar L) to obtain an oil phase solution for later use, wherein the mass fraction of the trimesoyl chloride in the oil phase solution is 0.2%.
1-butyl pyridine chloride is used as a functional solution for standby.
Firstly coating the water phase solution on a polysulfone support membrane, standing for 60s, pouring out the redundant water phase solution, and drying the membrane surface by cold air; and coating the oil phase solution on the blow-dried membrane surface, standing for 30s, pouring out the redundant oil phase solution, directly putting the membrane into a 90 ℃ forced air drying oven for heat treatment for 2min, and forming a loose first polyamide layer on the polysulfone support membrane. And coating the functional solution on the loose first polyamide layer, standing for 30s, removing the residual functional solution on the surface of the membrane, and then putting the membrane into an oven at 80 ℃ for heat treatment for 8min to obtain the composite membrane shown in figure 3. The removal rate of the composite membrane obtained by the comparative example on viruses and bacteria reaches more than 99.9 percent.
Referring to example 1, the composite membrane obtained in the present comparative example was subjected to a performance test, and the test results were: when the test object A is taken as inflow water, the retention rate of the composite membrane to sodium chloride is 58.7%, and the water flux is 88 LMH; when the test object B is taken as inflow water, the rejection rate of the composite membrane to magnesium sulfate is 98.6%, and the water flux is 52 LMH; when the test object C is taken as inflow water, the rejection rate of the composite membrane to sodium chloride is 38.8%, the rejection rate to magnesium sulfate is 99.3%, and the water flux is 47 LMH.
Comparative example 2
And uniformly mixing piperazine, triethylamine, decaglycerol and water to obtain an aqueous phase solution for later use, wherein the mass fraction of piperazine in the aqueous phase solution is 0.25%, the mass fraction of triethylamine in the aqueous phase solution is 1.0%, and the mass fraction of decaglycerol in the aqueous phase solution is 0.2%.
Uniformly mixing trimesoyl chloride (TMC) with an isoparaffin solvent (Isopar L) to obtain an oil phase solution for later use, wherein the mass fraction of the trimesoyl chloride in the oil phase solution is 0.15%.
Firstly coating the water phase solution on a polysulfone support membrane, standing for 60s, pouring out the redundant water phase solution, and drying the membrane surface by cold air; and coating the oil phase solution on the dried membrane surface, standing for 30s, pouring out the redundant oil phase solution, and directly putting the membrane into a forced air drying oven at 80 ℃ for heat treatment for 2min to obtain the composite membrane shown in figure 4. The removal rate of the composite membrane obtained by the comparative example on viruses and bacteria reaches more than 99.9 percent.
Referring to example 1, the composite membrane obtained in the present comparative example was subjected to a performance test, and the test results were: when the test object A is taken as inflow water, the retention rate of the composite membrane to sodium chloride is 13.1%, and the water flux is 162 LMH; when the test object B is taken as inflow water, the rejection rate of the composite membrane to magnesium sulfate is 55.2%, and the water flux is 98 LMH; when the test object C is taken as inflow water, the rejection rate of the composite membrane to sodium chloride is 1.7%, the rejection rate to magnesium sulfate is 57.9%, and the water flux is 89 LMH.
Comparative example 3
And uniformly mixing piperazine, triethylamine and water to obtain an aqueous phase solution for later use, wherein the mass fraction of the piperazine in the aqueous phase solution is 0.25%, and the mass fraction of the triethylamine in the aqueous phase solution is 1.0%.
Uniformly mixing trimesoyl chloride (TMC) with an isoparaffin solvent (Isopar L) to obtain an oil phase solution for later use, wherein the mass fraction of the trimesoyl chloride in the oil phase solution is 0.15%.
Firstly coating the water phase solution on a polysulfone support membrane, standing for 60s, pouring out the redundant water phase solution, and drying the membrane surface by cold air; and coating the oil phase solution on the dried membrane surface, standing for 30s, pouring out the redundant oil phase solution, and directly putting the membrane into a forced air drying oven at 80 ℃ for heat treatment for 2min to obtain the composite membrane shown in figure 5. The removal rate of the composite membrane obtained by the comparative example on viruses and bacteria reaches more than 99.9 percent.
Referring to example 1, the composite membrane obtained in the present comparative example was subjected to a performance test, and the test results were: when the test object A is taken as inflow water, the retention rate of the composite membrane to sodium chloride is 17.5%, and the water flux is 144 LMH; when the test object B is taken as inflow water, the rejection rate of the composite membrane to magnesium sulfate is 61.3%, and the water flux is 77 LMH; when the test object C is taken as inflow water, the rejection rate of the composite membrane to sodium chloride is 3.8%, the rejection rate to magnesium sulfate is 71.4%, and the water flux is 68 LMH.
Comparative example 4
And uniformly mixing piperazine, triethylamine and water to obtain an aqueous phase solution for later use, wherein the mass fraction of the piperazine in the aqueous phase solution is 0.25%, and the mass fraction of the triethylamine in the aqueous phase solution is 1.0%.
Uniformly mixing trimesoyl chloride (TMC) with an isoparaffin solvent (Isopar L) to obtain an oil phase solution for later use, wherein the mass fraction of the trimesoyl chloride in the oil phase solution is 0.15%.
And uniformly mixing piperazine and chlorinated 1-butyl-3-methylimidazolium salt to obtain a functional solution for later use, wherein the mass fraction of piperazine in the functional solution is 0.1%.
Firstly coating the water phase solution on a polysulfone support membrane, standing for 60s, pouring out the redundant water phase solution, and drying the membrane surface by cold air; and coating the oil phase solution on the blow-dried membrane surface, standing for 30s, pouring out the redundant oil phase solution, and directly putting the membrane into a forced air drying oven at 80 ℃ for heat treatment for 2min to obtain the prefabricated membrane. And coating the functional solution on the polyamide layer of the prefabricated membrane, standing for 30s, removing the residual functional solution on the surface of the membrane, and then putting the membrane into a 70 oven for heat treatment for 2min to obtain the composite membrane shown in figure 6. The removal rate of the composite membrane obtained by the comparative example on viruses and bacteria reaches more than 99.9 percent.
Referring to example 1, the composite membrane obtained in the present comparative example was subjected to a performance test, and the test results were: when the test object A is taken as inflow water, the retention rate of the composite membrane to sodium chloride is 66.4%, and the water flux is 44 LMH; when the test object B is taken as inflow water, the rejection rate of the composite membrane to magnesium sulfate is 90.5%, and the water flux is 33 LMH; when the test object C is taken as inflow water, the rejection rate of the composite membrane to sodium chloride is 44.3%, the rejection rate to magnesium sulfate is 92.5%, and the water flux is 52 LMH.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (11)

1. A method of making a composite membrane, comprising:
providing an aqueous phase solution and an oil phase solution, wherein the aqueous phase solution comprises polyglycerol and a first polyamine, and the oil phase solution comprises a polybasic acyl halide;
providing a support membrane, sequentially placing the aqueous phase solution and the oil phase solution on the surface of the support membrane, and performing first heat treatment to generate a first polyamide layer on the surface of the support membrane, wherein the first polyamide layer further comprises unreacted polyacyl halide; and
providing a functional solution, wherein the functional solution comprises a second polyamine and an ionic liquid, placing the functional solution on the surface of the first polyamide layer, which is far away from the support membrane, and carrying out second heat treatment to generate a second polyamide layer, wherein the second polyamide layer extends from the inside of the first polyamide layer to the surface of the first polyamide layer, which is far away from the support membrane, and the first polyamide layer and the second polyamide layer form a separation layer, so that a composite membrane is obtained.
2. The method for preparing the composite membrane according to claim 1, wherein the mass fraction of the polyglycerol in the aqueous solution is 0.1% to 0.5%.
3. The method of claim 1, wherein the polyglycerol is at least one member selected from the group consisting of diglycerol, triglycerol, pentaglycerol, and decaglycerol.
4. The method for preparing the composite membrane according to claim 1, wherein the mass fraction of the first polyamine in the aqueous phase solution is 0.1% to 1.0%, and the mass fraction of the second polyamine in the functional solution is 0.01% to 1.0%.
5. The method of claim 1, wherein the first polyamine and the second polyamine are independently at least one selected from piperazine and m-phenylenediamine.
6. The method of claim 1, wherein the ionic liquid is at least one selected from the group consisting of 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butylpyridinium bromide and 1-butylpyridinium chloride.
7. The method for preparing the composite membrane according to claim 1, wherein the mass fraction of the polybasic acid halide in the oil phase solution is 0.05% to 0.5%, and the polybasic acid halide is at least one selected from the group consisting of aromatic polybasic acid fluoride, aromatic polybasic acid chloride, aromatic polybasic acid bromide, aromatic polybasic acid iodide, aliphatic polybasic acid fluoride, aliphatic polybasic acid chloride, aliphatic polybasic acid bromide, and aliphatic polybasic acid iodide.
8. The method for preparing the composite membrane according to any one of claims 1 to 7, wherein the aqueous solution further comprises an acid scavenger, the mass fraction of the acid scavenger in the aqueous solution is 1% to 3%, and the acid scavenger is at least one selected from triethylamine and sodium hydroxide.
9. The method for preparing the composite membrane according to claim 8, wherein the material of the support membrane is at least one selected from polysulfone, polypropylene or polyacrylonitrile;
and/or a non-woven fabric layer is further provided and is arranged on the surface, far away from the separation layer, of the support membrane in a laminated mode.
10. A composite membrane prepared by the method of any one of claims 1 to 9.
11. Use of a composite membrane according to claim 10 in a water treatment device.
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JPH03137925A (en) * 1989-10-25 1991-06-12 Toyobo Co Ltd Post-treatment of reverse osmosis membrane
CN103071403A (en) * 2013-01-31 2013-05-01 北京碧水源膜科技有限公司 Double desalting layer composite reverse osmosis membrane and preparation method thereof
CN110585936A (en) * 2019-08-01 2019-12-20 蓝星（杭州）膜工业有限公司 Preparation method of high-performance reverse osmosis seawater film

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