CN112076714A - Method for preparing composite membrane by interfacial polymerization reaction and reaction device - Google Patents
Method for preparing composite membrane by interfacial polymerization reaction and reaction device Download PDFInfo
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- 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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- 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
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- B01D2323/42—Details of membrane preparation apparatus
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Abstract
The invention belongs to the field of membrane preparation, and particularly relates to a method for preparing a composite membrane by interfacial polymerization, wherein a support body is vertically fixed in a reaction container with a liquid containing cavity, the cavity of the reaction container is divided into two parts by the support body, a water phase and an organic phase are respectively added into the two parts of cavities, standing is carried out, after the two phases react and a polymer membrane layer is formed on the surface of the support body, the reaction is finished, and the obtained support body attached with the polymer membrane layer is the composite membrane; the aqueous phase and the organic phase are immiscible in solvent and the solutes in the two react with each other to form a polymer layer. The invention also relates to a reaction device for preparing the composite membrane by adopting the method for preparing the composite membrane by the interfacial polymerization reaction, which comprises a container and a clamping mechanism, wherein the clamping mechanism vertically fixes a support body in the container and divides a containing cavity of the container into a left part and a right part, and the two parts of containing cavities are respectively provided with a feed inlet.
Description
Technical Field
The invention belongs to the field of membrane preparation, and particularly relates to a method and a reaction device for preparing a composite membrane through interfacial polymerization.
Background
The interfacial polymerization reaction is a polycondensation reaction carried out at the interface of two mutually insoluble solutions in which two monomers are dissolved respectively (or at the interface organic phase side), and the polymer obtained by the reaction is insoluble in a solvent and precipitates in the interface. With the development of composite membrane technology, interfacial polymerization has been gradually applied to the preparation of composite membranes, i.e., microporous membranes or ultrafiltration membranes are used as support layers, and a dense homogeneous membrane is covered on the surface of the support layer by interfacial polymerization reaction to be used as a separation layer, so that the obtained membrane has a special separation effect.
"interfacial polymerization method" (tompezil et al, chemical evolution, vol. 9, 9 th 9 of 9/2007) describes a method for preparing a composite nanofiltration membrane by using interfacial polymerization, which is to form a thin dense layer on a porous support (microfiltration or ultrafiltration membrane) by using two monomers with high reactivity to perform polymerization reaction at the interface of two immiscible solvents, specifically: the support is first soaked in water solution containing active monomer to soak fully, the excessive solution is drained and the film is soaked in organic (oil) phase containing another active monomer. The two active monomers react with each other on the surface of the support to form a compact polymer skin layer, so that the permeability and the selectivity of the composite membrane are greatly improved. The key to the method is to select a reactive monomer with a suitable distribution coefficient and set a suitable diffusion rate to obtain the desired film surface compactness. However, the method of firstly soaking the aqueous phase and then soaking the organic phase has higher requirements on the reaction rate of the two monomers, and practical operation of an applicant verifies that the reaction process is complicated, the aqueous phase needs to be soaked firstly and then the organic phase needs to be soaked, the reaction process is extremely difficult to control, the film can be formed only within about 30 seconds, and particularly, the polymer film layer is an amorphous and relatively compact polyamide film layer without a regular pore structure, and the requirements on the permeability and the selectivity of the composite film are far from met.
English documents Can Li, Shuxuan Li, Long Tian, Jinmiao Zhang, Baowei Su, Michael Z.Hu, Consistent Organic Frames (COFs) -involved Thin Film Nanoparticles (TFN) membranes for high-fluorine Organic Solvent Nanoparticles (OSN). J.Membr.Sci 572(2019)520-531 describe the preparation of COFs membrane layer by interfacial polymerization, i.e. ordered porous organic Covalent polymer membrane layer, which is first hydrothermally synthesized, then superstripped into nanosheets, and finally vacuum filtered to form membrane. The prepared film layer really realizes an ordered porous structure, the permeability and the selectivity of the film layer are improved, but the preparation method can be realized only by high temperature and high pressure, and the equipment and the reaction conditions are difficult to achieve.
Therefore, in order to adapt to the application and development of interfacial polymerization reaction in the preparation of COFs composite membranes, it is imperative to find a simple and easily-realized method and equipment for preparing COFs composite membranes by interfacial polymerization reaction.
Disclosure of Invention
The invention aims to provide a method for preparing a composite membrane by interfacial polymerization, which can greatly simplify the reaction operation process and reduce the requirements on reaction conditions.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing composite membrane by interfacial polymerization reaction, fix the support body vertically in the reaction vessel with liquid cavity, and the support body divides the cavity of the said reaction vessel into two parts, add aqueous phase and organic phase in the two part cavities separately, left standstill, after two phases react and form the polymer membranous layer on the surface of support body, finish the reaction, the support body to get and adhere to polymer membranous layer is composite membrane; the aqueous phase and the organic phase are immiscible in solvent and the solutes in the two react with each other to form a polymer layer.
Wherein, the support is a microfiltration membrane or an ultrafiltration membrane.
By adopting the scheme for preparing the COFs (covalent organic frameworks) composite membrane, the two-phase solution is respectively arranged at the two sides of the support body, so that the sufficient supply of the active monomer at the interface of the two phases can be ensured, the thickness of the formed membrane layer is controllable, the harsh requirement on the reaction condition is not required, the requirement can be met only under the environment of normal temperature and normal pressure, the step of preparing the composite membrane by interfacial polymerization is greatly simplified, the requirement on equipment is reduced, the input cost is lower and safer, the polymer membrane layer formed on the support body is uniform and continuous, and the selectivity of the composite membrane is greatly improved.
Preferably, the aqueous phase comprises water, a monomer and a catalyst, wherein the monomer is a diamine compound, and the catalyst is a monobasic organic acid compound; the organic phase comprises a solvent and a solute, wherein the solvent is one or more of n-hexane, heptane, octane and nonane, and the solute is trimesic aldehyde and/or trialdehyde phloroglucinol. When the two-phase solution is subjected to interfacial polymerization reaction, the reaction rate is relatively slow, the reaction degree is controllable, and the time for terminating the reaction can be determined according to the requirement of the thickness of the polymer film layer, preferably, the reaction time is 0-72 hours, and generally, the thickness of the polymer film layer is about 100 nm. The longer the reaction time, the thickness of the resulting polymer film gradually increases, and as the film is formed, the amount of monomer that has reacted through the film from the two-phase monomers decreases, so the rate of increase in the film thickness decreases as the reaction time increases.
The concentration of diamine compounds in the water phase is 0.005-0.1 mol/L, and the concentration of monobasic organic acid compounds is 0.01-0.5 mol/L; the concentration of the organic phase is 0.0001-0.01 mol/L, the heights of the liquid surfaces of the two phases are the same, and the concentration of the water phase is greater than that of the organic phase.
The liquid level height is the same, the pressure in the two part containing cavities can be kept consistent, when the concentration of the water phase is slightly higher, the water phase can penetrate through the supporting body, and the interface of the two phases can be arranged on one side of the organic phase of the supporting body. The aqueous phase and the organic phase are added when the same, or the aqueous phase is added first and then the organic phase is added rapidly, and a film layer generated by the polymerization reaction of the monomers in the two phases is attached to one side surface of the organic phase of the support body. Of course, the greater the concentration of the two-phase solution, the faster the film formation rate, and the lower the concentration of the two phases, i.e., the faster the reaction rate to form the polymer film, to ensure the formation of a uniform and continuous interfacial polymer separation layer.
The invention also aims to provide a reaction device for preparing the composite membrane by adopting the interfacial polymerization reaction, which has simple structure, easy operation and low requirement on manufacturing materials.
In order to achieve the purpose, the invention adopts the technical scheme that: a reaction device adopting the method for preparing the composite membrane by the interfacial polymerization reaction comprises a container and a clamping mechanism, wherein the clamping mechanism vertically fixes a support body in the container and divides a containing cavity of the container into a left part and a right part, and the two parts of containing cavities are respectively provided with a charging hole.
Wherein, the support is a microfiltration membrane or an ultrafiltration membrane.
By adopting the interfacial polymerization reaction device, the support body divides the containing cavity of the container into two parts, and the water phase and the organic phase are respectively added into the two parts of the containing cavity, so that the solution at the two sides of the support body can be ensured to be supplied with the active monomer for polymerization reaction at any time, and the support body is fixed at the interface of the two phases, the formed film layer and the support body have high composite reliability, and the reaction device has simple structure and low cost investment.
Preferably, the container 10 is formed by two half bodies 11 and 12 having the same radial dimension and being clamped and connected by a clamping mechanism 20, and the support body a is interposed between the two half bodies 11 and 12. The design of the two half bodies is beneficial to the loading and unloading of the support body, the radial sizes of the two half bodies are the same, and the hydraulic stability of the two sides of the support body A is ensured.
The two half bodies 11 and 12 are provided with outward flanges 40 at the positions clinging to the container wall of the support body A, and the clamping mechanism 20 is clamped on the outward flanges 40 of the two half bodies 11 and 12. The outer flanging 40 of the two half bodies can firmly and stably clamp the outer edge of the support body A in the middle, and the clamping mechanism 20 is clamped on the outer flanging edge, so that the sealing effect at the edge of the support body can be ensured.
The two half bodies 11 and 12 are barrel-shaped, the barrel openings are arranged oppositely, and the wall of the barrel is provided with a feed inlet 30. Of course, the barrel diameters of the two barrel-shaped half bodies are the same, and the radial sizes of the flanging are also the same. When the device is used, the flanging of the barrel openings of the two half bodies are aligned, the support body is clamped at the barrel opening, and then the water phase and the organic phase can be respectively added into the two half bodies to carry out interfacial polymerization reaction.
The container 10 is made of an anti-corrosive transparent material. For example, quartz, which facilitates observation of the film formation on the support and facilitates termination of the reaction as needed.
Drawings
FIG. 1 is a schematic view of an interfacial polymerization apparatus according to the present invention.
In the figure: 10-container, 11, 12-container half body, 20-clamping mechanism, 30-charging opening, 40-flanging and A-supporting body
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
Example 1
The interfacial polymerization reaction device is adopted to prepare the composite membrane, the support body A adopts a polyacrylonitrile ultrafiltration membrane, the support body A is cut into a shape with the same size as the flanging of the two half bodies of the reaction device, and the reaction device is assembled for standby.
Preparing a solution: the water phase is an aqueous solution with the concentration of 0.0225mol/L of p-phenylenediamine and the concentration of 0.0675mol/L of p-toluenesulfonic acid, and the organic phase is an n-hexane solution with the concentration of 0.0075mol/L of trialdehyde phloroglucinol.
Adding the two-phase solution into the cavities on the two sides of the support A respectively as much as possible, keeping the liquid level heights on the two sides consistent, gradually forming a polymer film layer on one side of the organic phase solution of the support A, after reacting for 24 hours, ending the reaction, pouring the solutions on the two sides simultaneously, unloading the support A to obtain the prepared composite membrane, attaching a polymer film layer on one side surface of the composite membrane, wherein the thickness of the polymer film layer is 70nm, filtering the Congo red-ethanol solution with the concentration of 0.01mol/L by using the composite membrane, measuring the volume of the solution penetrating within a certain time, measuring the concentration of the Congo red-ethanol solution before and after filtering by using an ultraviolet spectrophotometer, calculating the permeability and rejection of the composite membrane to Congo red, and recording the calculated permeability and rejection into Table 1.
Example 2
The composite membrane is prepared by the same method as the embodiment 1, wherein the water phase is an aqueous solution with 0.05mol/L of biphenyldiamine concentration and 0.15mol/L of p-toluenesulfonic acid concentration, the organic phase is an n-hexane solution with 0.016mol/L of trialdehyde phloroglucinol concentration, the reaction time is 6 hours, and the thickness of the obtained composite membrane polymer membrane layer is 50 nm.
The composite membrane thus obtained was examined in the same manner as in example 1, and the examination results are shown in Table 1.
Example 3
The composite membrane is prepared by the same method as the embodiment 1, the water phase is an aqueous solution with the concentration of the biphenyldiamine being 0.04mol/L and the concentration of the p-toluenesulfonic acid being 0.12mol/L, the organic phase is an n-hexane solution with the concentration of the trialdehyde phloroglucinol being 0.011mol/L, the reaction time is 4 hours, and the thickness of the obtained composite membrane polymer membrane layer is 30 nm.
The composite membrane thus obtained was examined in the same manner as in example 1, and the examination results are shown in Table 1.
TABLE 1 examination results of the composite membranes obtained in examples 1 to 3
| Coefficient of penetration (L/m)2·h·bar) | Retention (%) | |
| Example 1 | 75.8 | 99.5 |
| Example 2 | 88.4 | 99.6 |
| Example 3 | 95.6 | 99.5 |
As can be seen from the data in Table 1, the rejection rate of the COFs composite membrane prepared by the scheme of the invention to the filtrate is greatly improved.
Claims (10)
1. A method for preparing a composite membrane by interfacial polymerization reaction is characterized in that: vertically fixing a support body in a reaction container with a liquid containing cavity, dividing the containing cavity of the reaction container into two parts by the support body, respectively adding a water phase and an organic phase into the two parts of the containing cavity, standing, finishing the reaction after the two phases react and forming a polymer film layer on the surface of the support body, and obtaining the support body attached with the polymer film layer, namely a composite film; the solvents of the aqueous phase and the organic phase are immiscible and the solutes in the two react with each other to form a polymer layer.
2. The method of preparing a composite membrane by interfacial polymerization according to claim 1, wherein: the water phase comprises water, a monomer and a catalyst, wherein the monomer is a diamine compound, and the catalyst is a monobasic organic acid compound; the organic phase comprises a solvent and a solute, wherein the solvent is one or more of n-hexane, heptane, octane and nonane, and the solute is trimesic aldehyde and/or trialdehyde phloroglucinol.
3. A method of preparing a composite membrane according to claim 2, wherein: the concentration of diamine compounds in the water phase is 0.005-0.1 mol/L, and the concentration of monobasic organic acid compounds is 0.01-0.5 mol/L; the concentration of the organic phase is 0.0001-0.01 mol/L, and the concentration of the water phase is greater than that of the organic phase.
4. The method of preparing a composite membrane according to claim 1, wherein: the aqueous phase and the organic phase are added at the same time, or the aqueous phase is added first and then the organic phase is added rapidly.
5. The method of preparing a composite membrane according to claim 1, wherein: the reaction time is 0-72 hours.
6. An interfacial polymerization apparatus for preparing a composite membrane by interfacial polymerization according to any one of claims 1 to 5, wherein: the device comprises a container (10), wherein a clamping mechanism (20) which vertically fixes a support body (A) in a containing cavity is arranged on the container (10), the containing cavity of the container (10) is divided into a left part and a right part by the vertical support body (A), and the containing cavities of the two parts are respectively provided with a feed inlet (30).
7. The interfacial polymerization apparatus of claim 6, wherein: the container (10) is formed by clamping and connecting two half bodies (11, 12) with the same radial dimension through a clamping mechanism (20), and the support body (A) is clamped between the two half bodies (11, 12).
8. The interfacial polymerization apparatus of claim 7, wherein: the two half bodies (11 and 12) are provided with outward flanges (40) at the positions clinging to the container wall of the support body (A), and the clamping mechanism (20) is clamped on the outward flanges (40) of the two half bodies (11 and 12).
9. The interfacial polymerization apparatus of claim 7, wherein: the two half bodies (11, 12) are barrel-shaped, the barrel openings are arranged oppositely, and a charging opening (30) is arranged on the barrel wall.
10. The interfacial polymerization apparatus of claim 6, wherein: the container (10) is made of an anti-corrosion transparent material.
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| CN113070022A (en) * | 2021-03-22 | 2021-07-06 | 齐齐哈尔大学 | Batch circulating type ultrathin film unfolding preparation device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113070022A (en) * | 2021-03-22 | 2021-07-06 | 齐齐哈尔大学 | Batch circulating type ultrathin film unfolding preparation device |
| CN113070022B (en) * | 2021-03-22 | 2023-02-17 | 齐齐哈尔大学 | Batch circulating type ultrathin film unfolding preparation device |
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