CN110935316A - Preparation method of ultrahigh-flux composite forward osmosis membrane - Google Patents
Preparation method of ultrahigh-flux composite forward osmosis membrane Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- 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
- B01D71/48—Polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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Abstract
The invention discloses a preparation method of an ultrahigh flux composite forward osmosis membrane. The preparation method comprises the following steps: (i) respectively preparing polyamine water phase solution with the mass percent concentration of 0.001-0.5% and aromatic acyl chloride oil phase solution with the mass percent concentration of 0.001-0.1%; (ii) uniformly dispersing the polyamine aqueous phase solution on a non-woven fabric support layer to obtain an amine solution layer, wherein the contact time is 5-120 seconds, removing the redundant aqueous phase solution, and draining; (iii) (iii) uniformly dispersing the prepared aromatic acyl chloride oil phase solution on the base membrane treated in the step (ii), and carrying out interfacial polymerization reaction for 5-30 seconds to form a polyamide separation layer; (iv) (iv) subjecting the membrane obtained in step (iii) to heat treatment to remove the solvent, thereby obtaining the composite forward osmosis membrane. The preparation method provided by the invention can improve the flux and stability of the composite forward osmosis membrane while maintaining the high salt cut-off rate of the composite forward osmosis membrane, reduce the material consumption and energy consumption in the membrane preparation process, and save the cost.
Description
(I) technical field
The invention belongs to the technical field of membrane separation, and particularly relates to a method for preparing a composite forward osmosis membrane by utilizing interfacial polymerization.
(II) background of the invention
Forward Osmosis (FO) technology takes osmotic pressure difference or chemical potential difference on two sides of a membrane as a driving force, and has great advantages in the aspects of reducing energy consumption, reducing pollution, improving recovery rate and the like. However, one of the bottlenecks of forward osmosis research is the concentration polarization phenomenon generated in the porous support layer, which greatly reduces the separation performance of the membrane. Therefore, it is highly desirable to find a support layer having high permeability while ensuring the mechanical strength and chemical resistance of the membrane. Secondly, the interfacial polymerization method is used for preparing the polyaromatic amide separation layer, namely, the polycondensation or polymerization reaction of two monomers with high reaction activity is carried out at the interface based on the phase interface polymerization principle. However, the main drawbacks of this method are: the amine solution required is usually super oxidative, which brings great difficulty to the subsequent treatment of the composite membrane, including rinsing and storage of the membrane. Therefore, we consider solving the above problem without sacrificing the salt cut-off.
Disclosure of Invention
The invention aims to provide a preparation method of a composite forward osmosis membrane, which can improve the flux and stability of the membrane, reduce the material consumption and energy consumption in the membrane preparation process and save the cost while maintaining the high salt cut-off rate of the composite forward osmosis membrane.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a composite forward osmosis membrane comprises the following steps:
(i) respectively preparing polyamine water phase solution with the mass percent concentration of 0.001-0.5% and aromatic acyl chloride oil phase solution with the mass percent concentration of 0.001-0.1%;
(ii) uniformly dispersing the polyamine aqueous phase solution on a non-woven fabric support layer to obtain an amine solution layer, wherein the contact time is 5-120 seconds, removing the redundant aqueous phase solution, and draining;
(iii) (iii) uniformly dispersing the prepared aromatic acyl chloride oil phase solution on the base membrane treated in the step (ii), and carrying out interfacial polymerization reaction for 5-30 seconds to form a polyamide separation layer;
(iv) (iv) subjecting the membrane obtained in step (iii) to heat treatment to remove the solvent, thereby obtaining the composite forward osmosis membrane.
According to the preparation method of the composite forward osmosis membrane, firstly, interfacial polymerization is directly carried out on the surface of the polyester non-woven fabric, an ultrafiltration middle layer is removed, and internal concentration polarization is greatly reduced; the polyester non-woven fabric is selected as the supporting layer, because the polyester non-woven fabric has a highly open and mutually communicated pore structure, a certain effect can be achieved in the aspect of reducing the internal concentration polarization; meanwhile, the surface of the non-woven fabric is smooth, so that disordered accumulation of polymers in the film preparation process can be effectively avoided; the requirements of operation can also be met in terms of mechanical strength. Secondly, in the process of preparing the polyamide layer by applying an interfacial polymerization method, the common amine solution has strong oxidizability, and after the interfacial polymerization reaction, the redundant amine solution is attached to the polyamide layer and is difficult to be completely rinsed away, so that the prepared composite forward osmosis membrane is very easy to oxidize and blacken in the storage process. Therefore, the invention utilizes the low-concentration monomer to directly and rapidly carry out interfacial polymerization on the surface of the polyester non-woven fabric to generate the ultrathin polyaromatic amide separation layer, removes the ultrafiltration intermediate layer which can cause an internal concentration difference structure, and simultaneously avoids the oxidative denaturation of the composite membrane.
Preferably, the polyamine is selected from one or any combination of several of the following in any proportion: m-phenylenediamine, o-phenylenediamine, pyromellitic triamine, diethylenetriamine and piperazine.
Preferably, the concentration of the aqueous polyamine solution is from 0.005% to 0.1%, more preferably 0.01%. In the invention, the concentration of the polyamine aqueous phase solution is particularly preferably 0.01%, and the concentration of the aromatic acyl chloride oil phase solution is preferably 0.05%.
The invention has no special requirement on the volume dosage of the polyamine aqueous phase solution on the non-woven fabric support layer, and the conventional dosage is adopted, for example, the volume dosage is 0.25-0.45mL/cm based on the area of the non-woven fabric support layer2. In the invention, the polyamine aqueous phase solution and the non-woven fabric areThe contact time of the support layer is sufficient to allow sufficient contact between the two layers, and the length of contact time generally does not have a significant effect on the performance of the film.
Preferably, the aromatic acyl chloride is selected from one or any combination of several of the following in any proportion: trimesoyl chloride, isophthaloyl dichloride, terephthaloyl dichloride and polybasic aromatic sulfonyl chloride.
Preferably, the solvent used for preparing the oil phase solution of aromatic acyl chloride is selected from one or a mixture of any of the following in any proportion: n-hexane, isododecane, decane, Isopar G.
The volume dosage of the aromatic acyl chloride oil phase solution on the non-woven fabric is not particularly required, and the conventional dosage is adopted, for example, the volume dosage is 0.25-0.45mL/cm calculated by the area of the polyester non-woven fabric supporting layer2。
In step (iii) of the present invention, the interfacial polymerization time is 5 to 30 seconds, and the composite forward osmosis membrane obtained in this time range can basically meet the required performance requirements, and preferably, the interfacial polymerization time is 10 to 30 seconds.
Preferably, the heat treatment conditions in step (iv) are: drying for 1-20 minutes at 50-100 ℃.
The polyester nonwoven fabric of the present invention may be a commercially available one.
The composite forward osmosis membrane prepared by the invention can be used for emergency water bags, fruit juice concentration, pharmacy, plant protection boxes, seawater desalination, hard water softening or industrial wastewater treatment.
Compared with the prior art, the invention has the beneficial effects that: the polyester non-woven fabric used in the invention has a highly open and mutually communicated pore structure, and the interfacial polymerization is directly carried out on the surface of the polyester non-woven fabric, so that an ultrafiltration intermediate layer is removed, and the internal concentration polarization is greatly reduced; the monomer concentration is reduced, the redundant monomer attached to the surface of the polyamide layer is reduced, and the oxidative denaturation of the composite forward osmosis membrane is avoided. Finally, the high salt cut-off rate of the composite forward osmosis membrane is maintained, the high flux and stability of the membrane are improved, the material consumption and energy consumption in the membrane preparation process are reduced, and the cost is saved.
(IV) description of the drawings
FIGS. 1-a and 1-b are structural views of a composite membrane prepared in comparative example 1.
FIGS. 2-a and 2-b are structural diagrams of the composite membrane prepared in example 1.
FIGS. 3-a and 3-b are structural diagrams of the composite membrane prepared in example 2.
FIG. 4 is a graph showing the comparison of the degree of oxidative denaturation of a composite membrane.
(V) detailed description of the preferred embodiments
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Percentages and fractions are volume percentages and volume fractions unless otherwise indicated.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
The following examples of the invention are further illustrated:
typical comparative example 1:
step (1): preparing a m-phenylenediamine solution with the mass fraction of 2%, wherein a solvent is deionized water, and the solution is used as a water phase for later use;
step (2): preparing 0.1% by mass of trimesoyl chloride solution, wherein a solvent is normal hexane, and the solution is used as an oil phase for later use;
and (3): uniformly dispersing 60mL of the water phase obtained in the step (1) on a 13X 13cm polyester non-woven fabric, contacting for 3 minutes, removing the redundant m-phenylenediamine solution, and draining;
and (4): uniformly dispersing 60mL of the oil phase obtained in the step (2) on a m-phenylenediamine solution layer with the thickness of 13 x 13cm, and contacting for 2 minutes to obtain a polyamide layer;
and (5): and (4) carrying out heat treatment on the membrane prepared in the step (4), and drying for 15 minutes at the temperature of 80 ℃ to obtain the composite forward osmosis membrane.
The film structure was observed under an electron microscope, and as a result, the polyamide separation layer was thick as shown in FIG. 1. Meanwhile, as shown in fig. 4 (leftmost), the membranes were separately stored in deionized water, and it was found that the composite forward osmosis membrane was significantly oxidized to yellow after 1 day.
The forward osmosis membrane prepared in this example was loaded into a membrane performance evaluation apparatus, and then the forward osmosis FO membrane flux measured using 2mol/L aqueous sodium chloride solution as draw solution and purified water as stock solution was 45L/m2H, salt rejection 99.87%.
Exemplary embodiment 1:
step (1): preparing a m-phenylenediamine solution with the mass fraction of 0.01%, wherein the solvent is deionized water, and the solution is used as a water phase for later use;
step (2): preparing 0.05% by mass of trimesoyl chloride solution, taking n-hexane as a solvent, and taking the solution as an oil phase for later use;
and (3): uniformly dispersing 60mL of the water phase obtained in the step (1) on a 13X 13cm polyester non-woven fabric, contacting for 60 seconds, removing the redundant m-phenylenediamine solution, and draining;
and (4): dispersing 60mL of the oil phase obtained in the step (2) on a 13 x 13cm m-phenylenediamine solution layer, and contacting for 30 seconds to obtain an ultrathin polyamide layer;
and (5): and (4) carrying out heat treatment on the membrane prepared in the step (4), and drying for 15 minutes at the temperature of 60 ℃ to obtain the ultrathin composite forward osmosis membrane.
The membrane structure was observed under an electron microscope, and as a result, as shown in fig. 2, a thinner polyamide separation layer was formed under the alkane rinsing condition, and at the same time, as shown in fig. 4 (middle), when the membrane was stored in deionized water, it was found that the composite forward osmosis membrane did not significantly change after 30 days.
The forward osmosis membrane prepared in this example was loaded into a membrane performance evaluation apparatus, and then forward osmosis FO membrane flux of 1125L/m was measured using 2mol/L aqueous sodium chloride solution as draw solution and purified water as stock solution2H, salt rejection 99.85%.
Exemplary embodiment 2:
step (1): preparing 0.01 mass percent piperazine solution, wherein the solvent is deionized water, and the solution is used as a water phase for later use;
step (2): preparing 0.05 percent by mass of trimesoyl chloride solution, taking isododecane as a solvent, and taking the solution as an oil phase for later use;
and (3): uniformly dispersing 60mL of the water phase obtained in the step (1) on a 13X 13cm polyester non-woven fabric, contacting for 60 seconds, removing the redundant piperazine solution, and draining;
and (4): dispersing 60mL of the oil phase obtained in the step (2) on a 13X 13cm piperazine solution layer, and contacting for 30 seconds to obtain an ultrathin polyamide layer;
and (5): and (4) carrying out heat treatment on the membrane prepared in the step (4), and drying for 15 minutes at the temperature of 60 ℃ to obtain the ultrathin composite forward osmosis membrane.
Observing the membrane structure under an electron microscope, the result is shown in fig. 2, a thinner polyamide separation layer is formed under the alkane leaching condition, meanwhile, as shown in fig. 4 (rightmost), the composite forward osmosis membrane is kept in deionized water, and no obvious change is found after thirty days.
The forward osmosis membrane prepared in this example was placed in a membrane performance evaluation apparatus, and then the forward osmosis FO membrane flux was measured at 1507L/m using a 2mol/L aqueous solution of sodium chloride as a draw solution and purified water as a stock solution2H, salt rejection 99.56%.
Exemplary embodiments 3 to 5
The flux and salt cut-off of the forward osmosis membrane prepared in the same manner as in example 1 except that the concentration of the m-phenylenediamine solution in example 1 was changed are shown in Table 1:
TABLE 1
| Examples | MPD concentration | Water flux | Salt cutting machineRate of change |
| 3 | 0.005％ | 1321 | 98.46％ |
| 4 | 0.1％ | 422 | 99.24％ |
| 5 | 0.5％ | 48 | 99.45％ |
The detection result shows that the performance of the ultra-high flux forward osmosis membrane prepared by the invention is superior to that of the forward osmosis membrane prepared by the traditional reverse osmosis membrane preparation method, and the high-performance forward osmosis membrane prepared by the invention has better popularization and application prospects and industrialization value.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (9)
1. A preparation method of a composite forward osmosis membrane comprises the following steps:
(i) respectively preparing polyamine water phase solution with the mass percent concentration of 0.001-0.05% and aromatic acyl chloride oil phase solution with the mass percent concentration of 0.001-0.1%;
(ii) uniformly dispersing the polyamine aqueous phase solution on a non-woven fabric support layer to obtain an amine solution layer, wherein the contact time is 5-120 seconds, removing the redundant aqueous phase solution, and draining;
(iii) (iii) uniformly dispersing the prepared aromatic acyl chloride oil phase solution on the base membrane treated in the step (ii), and carrying out interfacial polymerization reaction for 5-30 seconds to form a polyamide separation layer;
(iv) (iv) subjecting the membrane obtained in step (iii) to heat treatment to remove the solvent, thereby obtaining the composite forward osmosis membrane.
2. The method of claim 1, wherein: the polyamine is selected from one or any combination of several of the following in any proportion: m-phenylenediamine, o-phenylenediamine, pyromellitic triamine, diethylenetriamine and piperazine.
3. The method of claim 1, wherein: the concentration of the polyamine aqueous phase solution is 0.005-0.1%.
4. The method of claim 1, wherein: the concentration of the aqueous polyamine solution was 0.01%.
5. The method of claim 1, wherein: the concentration of the polyamine aqueous phase solution is 0.01 percent, and the concentration of the aromatic acyl chloride oil phase solution is 0.05 percent.
6. The method according to any one of claims 1 to 5, wherein: the aromatic acyl chloride is selected from one or a combination of any several of the following components in any proportion: trimesoyl chloride, isophthaloyl dichloride, terephthaloyl dichloride and polybasic aromatic sulfonyl chloride.
7. The method according to any one of claims 1 to 5, wherein: the solvent used for preparing the aromatic acyl chloride oil phase solution is selected from one or a mixture of any of the following components in any proportion: n-hexane, isododecane, decane, Isopar G.
8. The method according to any one of claims 1 to 5, wherein: the interfacial polymerization time is 10-30 seconds.
9. The method according to any one of claims 1 to 5, wherein: the heat treatment conditions in step (iv) are as follows: drying for 1-20 minutes at 50-100 ℃.
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