Preparation process of organic composite material with ultrahigh salt resistance

Abstract

The invention discloses a preparation process of an organic composite material with ultrahigh salt resistance. Comprising the following steps: calculating and simulating to obtain a salient point form and a salient point distance h in the micro-morphology of the film; and calculating to obtain the average diameter D of the particles forming the salient points. The dispersed polytetrafluoroethylene particles are subjected to thermocuring treatment and deagglomeration treatment, and treated particles a are obtained; according to h between the salient points, obtaining the configuration proportion of the treated particles a and the dispersed PTFE particles, mixing and stirring according to the proportion, and then carrying out fibrosis treatment to obtain treated particles b; placing the two kinds of particles in layers, and forming an asymmetric film through a stretching process; mixing a fluorine monomer, an electrostatic conduction material and an alcohol solvent to obtain a pre-prepared solution; spraying the prefabricated solution on the surface of a base material to obtain a treated base material; and hot-pressing and laminating the asymmetric film on a base material to form the organic composite material. The membrane material is suitable for flue gas filtration systems in different industries, and is especially suitable for purification of medium and low temperature flue gas systems with high salting-out degree.

Description

Technical Field

[0001] The present invention relates to the field of preparation of novel functional materials, and particularly to a preparation process of an organic composite material with ultra-high salt resistance performance. Background Art

[0002] The flue gas and dust generated in the processes of steel smelting, coal-fired power generation, chemical reactions, etc. in industries such as metallurgy, electric power, and chemical industry contain a large amount of acidic gases. Usually, ammonia water is first used to neutralize the acidic gas components in the flue gas and dust, and then heat exchange, dust removal, etc. are performed on the neutralized flue gas and dust, and finally it is discharged to the atmosphere. However, the flue gas and dust after acid-base neutralization contain ammonia components. When the temperature of the flue gas and dust fluctuates, ammonium salt crystals are easily formed; at the same time, a part of the ammonium salt will dissolve into the water vapor to form a viscous acidic liquid, which is easy to adhere to the inner surface of the heat exchange equipment and dust removal equipment in the low-temperature section and the outer surface of the filter material. The crystallization and caking of ammonium salts and the adhesion of acidic liquids easily lead to an increase in the operating resistance, and the dust removal equipment needs to be cleaned regularly, but it also increases the cost of tail gas treatment. In addition, the waste water generated by cleaning forms secondary pollution. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation process of an organic composite material with ultra-high salt resistance performance, which solves the problems of easy salt crystallization and caking on the surface of the filter material and increased operating resistance in the filtration of salt-containing flue gas.

[0004] The technical solution of the present invention is as follows: A preparation process of an organic composite material with ultra-high salt resistance performance, the process steps are as follows: (1) Calculate and simulate the bump morphology and bump spacing h in the microscopic morphology affecting the surface roughness; (2) Calculate the average diameter D of the bump particles formed according to the bump morphology; (3) Perform heat curing treatment and deagglomeration treatment on the dispersed polytetrafluoroethylene (PTFE) particles to obtain treated particles a with a high hardness and an average diameter D; (4) According to the h between the bumps, obtain the mixing ratio of the treated particles a and the dispersed PTFE particles. After mixing and stirring the two according to the ratio, perform partial fibrillation treatment. The morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are fibrillated under force to obtain treated particles b; (5) Place the treated particles b and PTFE particles in layers, and form an asymmetric membrane through pushing, rolling, and stretching; (6) Mix a fluorine monomer, an electrostatic conduction material, and an alcohol solvent to obtain a prefabricated solution;

[0005] (7) Spray the prefabricated solution on the surface of the substrate to obtain a treated substrate; (8) Thermally press and laminate the asymmetric membrane onto the treated substrate to form an organic composite material with ultra-high salt resistance. Among them: In step (1), the bump morphologies affecting the surface roughness obtained through computational simulation include circular, elliptical, and columnar structures. The range of the bump spacing h is between 0.02 - 195 microns.

[0006] In step (2), according to the bump morphology, the average diameter D of the bump particles is calculated, and its range is between 0.01 - 100 microns.

[0007] The thermal curing treatment methods in step (3) include, but are not limited to, heat treatment in a high-temperature box, hot pressing with high-temperature double rollers, infrared point-to-point radiation curing, etc.; The curing temperature of the thermal curing treatment in step (3) is 120 - 400 °C; The deflocculation treatment methods in step (3) include, but are not limited to, high-frequency mechanical oscillation, ultrasonic oscillation, electromagnetic oscillation, etc.; The weight ratio of the treated particle a to the PTFE particle in step (4) is 1:50 ~ 20:50, and the mixing time is 0.5 - 10 minutes; In step (5), the treated particle b is placed on top of the PTFE particles. The treated particle b is distributed in one layer, and the number of layers of PTFE particles is two or more.

[0008] The fluorine-based monomers in step (6) include, but are not limited to, one or more of perfluoroacrylate, ethyl perfluoropropionate, methyl perfluoroacetate, perfluoropolyether, perfluorodimethyl ether, perfluoroalkoxysulfonic acid; The electrostatic conduction materials in step (6) include, but are not limited to, one or more of aluminum nitride, silicon dioxide, silicon carbide.

[0009] The mixing ratio of the fluorine-based monomer to the alcohol solvent in step (6) is between 0.5:10 and 5:10, The mixing ratio of the semiconductor material to the alcohol solvent is between 0.1:10 and 1:10; The prefabricated solution spraying methods in step (7) include, but are not limited to, unidirectional spraying, bidirectional spraying, electrostatic spraying, etc.

[0010] Advantages of the present invention: 1. The organic composite membrane prepared by the present invention has excellent properties such as ultra-high salt resistance, high separation precision, and large gas flux, and is suitable for the flue gas filtration systems in different industries, especially for the purification of medium and low-temperature flue gas systems with high salting-out degree.

[0011] 2. The preparation process of the present invention is simple, easy to operate, and convenient for industrial production. Description of the Drawings

[0012] Figure 1 It is the electron micrograph of the asymmetric membrane in Example 6.

[0013] Figure 2 It is the electron micrograph after the prefabricated solution in Example 6 is sprayed on the substrate.

[0014] Figure 3 It is the electron micrograph of the organic composite material prepared in Example 6. Detailed implementation manners

[0015] The present invention will be further explained below in conjunction with embodiments. The following embodiments are only used to illustrate the present invention, but do not limit the implementation scope of the present invention. Example 1

[0016] Through computational simulation, it is obtained that the bump shape in the microscopic topography affecting the surface roughness is elliptical, the bump spacing h is 195 microns, and the average diameter D of the particles forming the bumps is calculated to be 100 microns.

[0017] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to infrared point-to-point radiation curing at a curing temperature of 200 °C, and then processed by high-frequency mechanical oscillation to obtain processed particles a with an average diameter D of 100 microns; the processed particles a and the dispersed PTFE particles are mixed and stirred in a mass ratio of 1:50 for 10 minutes, and then subjected to partial fibrillation treatment. The shape of the processed particles a remains unchanged, and the dispersed PTFE particles are fibrillated under force to obtain processed particles b; the processed particles b and the dispersed PTFE particles are placed in layers, with one layer of processed particles b and two layers of PTFE particles, and an asymmetric membrane is formed by pushing, rolling, and stretching.

[0018] Ethyl perfluoropropionate monomer, aluminum nitride and ethanol are mixed in a mass ratio of 0.5:0.1:10 to obtain a prefabricated solution; the prefabricated solution is attached to the surface of the substrate through a one-way spraying process to obtain a processed substrate.

[0019] The asymmetric membrane is laminated on the processed substrate to form an organic composite material 1 with ultra-high salt resistance performance. Example 2

[0020] Through computational simulation, it is obtained that the bump shape in the microscopic topography affecting the surface roughness is elliptical, the bump spacing h is 10 microns, and the average diameter D of the particles forming the bumps is calculated to be 15 microns.

[0021] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to infrared point-to-point radiative heat curing at a curing temperature of 200 °C, and then processed by high-frequency mechanical oscillation to obtain processed particles a with an average diameter D of 15 microns; the processed particles a and the dispersed PTFE particles are mixed and stirred in a mass ratio of 10:50 for 2 minutes, and then subjected to partial fibrillation treatment. The morphology of the processed particles a remains unchanged, and the dispersed PTFE particles are fibrillated under force to obtain processed particles b; the processed particles b and the dispersed PTFE particles are placed in layers, with one layer of processed particles b and four layers of PTFE particles, and an asymmetric membrane is formed by pushing, rolling, and stretching.

[0022] Ethyl perfluoropropionate monomer, aluminum nitride, and isopropanol are mixed in a mass ratio of 1:0.5:10 to obtain a prefabricated solution; the prefabricated solution is attached to the surface of the substrate through a one-way spraying process to obtain a processed substrate.

[0023] The asymmetric membrane is laminated on the processed substrate to form an organic composite material 2 with ultra-high salt resistance. Example 3

[0024] Through computational simulation, it is obtained that the shape of the protrusions in the microscopic morphology affecting the surface roughness is elliptical, and the protrusion spacing h is 1 micron. The average diameter D of the particles forming the protrusions is calculated to be 1.3 microns.

[0025] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to high-temperature box heat curing at a curing temperature of 120 °C, and then processed by ultrasonic oscillation to obtain processed particles a with an average diameter D of 1.3 microns; the processed particles a and the dispersed PTFE particles are mixed and stirred in a mass ratio of 20:50 for 0.5 minutes, and then subjected to partial fibrillation treatment. The morphology of the processed particles a remains unchanged, and the dispersed PTFE particles are fibrillated under force to obtain processed particles b; the processed particles b and the dispersed PTFE particles are placed in layers, with one layer of processed particles b and two layers of PTFE particles, and an asymmetric membrane is formed by pushing, rolling, and stretching.

[0026] Methyl perfluoroacetate monomer, aluminum nitride, and ethylene glycol are mixed in a mass ratio of 5:1:10 to obtain a prefabricated solution; the prefabricated solution is attached to the surface of the substrate through a one-way spraying process to obtain a processed substrate.

[0027] The asymmetric membrane is laminated on the processed substrate to form an organic composite material 3 with ultra-high salt resistance. Example 4

[0028] Through computational simulation, it is obtained that the shape of the protrusions in the microscopic morphology affecting the surface roughness is elliptical, and the protrusion spacing h is 0.5 micron. The average diameter D of the particles forming the protrusions is calculated to be 1 micron.

[0029] The dispersed polytetrafluoroethylene (PTFE) particles are heat-treated in a high-temperature box, with the curing temperature being 400 °C, and then processed by ultrasonic oscillation to obtain treated particles a; the treated particles a with an average diameter D of 1 μm and the dispersed PTFE particles are mixed and stirred in a mass ratio of 10:50 for 5 minutes, and then subjected to partial fibrillation treatment. The morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are fibrillated under force to obtain treated particles b; the treated particles b and the dispersed PTFE particles are placed in layers, with one layer of treated particles b and four layers of PTFE particles, and an asymmetric membrane is formed by pushing, rolling, and stretching.

[0030] Ethyl perfluoropropionate monomer, silica, and isopropanol are mixed in a mass ratio of 0.5:0.1:10 to obtain a prefabricated solution; the prefabricated solution is attached to the surface of the substrate through a one-way spraying process to obtain a treated substrate.

[0031] The asymmetric membrane is laminated on the treated substrate to form an organic composite material 4 with ultra-high salt resistance performance. Example 5

[0032] Through computational simulation, it is obtained that the shape of the bumps in the microscopic morphology affecting the surface roughness is elliptical, and the bump spacing h is 0.1 μm. The average diameter D of the particles forming the bumps is calculated to be 0.15 μm.

[0033] The dispersed polytetrafluoroethylene (PTFE) particles are heat-cured by high-temperature double-roll hot pressing, with the curing temperature being 300 °C, and then processed by electromagnetic oscillation to obtain treated particles a with an average diameter D of 0.15 μm; the treated particles a and the dispersed PTFE particles are mixed and stirred in a mass ratio of 5:50 for 5 minutes, and then subjected to partial fibrillation treatment. The morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are fibrillated under force to obtain treated particles b; the treated particles b and the dispersed PTFE particles are placed in layers, with one layer of treated particles b and four layers of PTFE particles, and an asymmetric membrane is formed by pushing, rolling, and stretching.

[0034] Perfluoropolyether monomer, silicon carbide, and ethanol are mixed in a mass ratio of 1:0.5:10 to obtain a prefabricated solution; the prefabricated solution is attached to the surface of the substrate through a one-way spraying process to obtain a treated substrate.

[0035] The asymmetric membrane is laminated on the treated substrate to form an organic composite material 5 with ultra-high salt resistance performance. Example 6

[0036] Through computational simulation, it is obtained that the shape of the bumps in the microscopic morphology affecting the surface roughness is elliptical, and the bump spacing h is 0.02 μm. The average diameter D of the particles forming the bumps is calculated to be 0.01 μm.

[0037] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to high-temperature double-roll hot pressing and thermal curing at a curing temperature of 300 °C, and then treated by electromagnetic oscillation to obtain treated particles a with an average diameter D of 0.01 micrometers; the treated particles a and the dispersed PTFE particles are mixed and stirred in a mass ratio of 15:50 for 5 minutes, and then subjected to partial fibrillation treatment. The morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are fibrillated under force to obtain treated particles b; the treated particles b and the dispersed PTFE particles are placed in layers, with one layer of treated particles b and four layers of PTFE particles, and an asymmetric membrane is formed by extrusion, calendering, and stretching.

[0038] The perfluorodimethyl ether monomer, aluminum nitride, and isopropanol are mixed in a mass ratio of 3:0.5:10 to obtain a prefabricated solution; the prefabricated solution is attached to the surface of the substrate by a unidirectional spraying process to obtain a treated substrate.

[0039] The asymmetric membrane is laminated on the treated substrate to form an organic composite material 6 with ultra-high salt resistance.

[0040] For the organic composite material with ultra-high salt resistance prepared in the above examples, a salt spray test of continuous spraying with a 5% sodium chloride neutral solution for 96 h is carried out, and the performance test data of the membrane material before and after the salt spray test are shown in Table 1 below.

[0041] After calculation, the decrease in air permeability of the above organic composite membrane material after the salt spray test is less than 10%, and the increase in filtration resistance is less than 15%. Compared with the blank sample with a 33% decrease in air permeability and a 36% increase in filtration resistance, the organic composite material prepared in the example has obvious salt resistance and can ensure that the membrane material continuously has a high air permeability.

[0042] Table 1 Performance test of organic composite material with ultra-high salt resistance

Claims

1. A process for preparing an organic composite material with ultra-high salt resistance, characterized in that: The preparation steps are as follows: (1) The convex morphology and convex spacing h in the microscopic morphology that affect the surface roughness are obtained through computational simulation; (2) Based on the convex morphology, the average diameter D of the convex particles is calculated; (3) subjecting dispersed polytetrafluoroethylene (PTFE) particles to a thermal curing treatment and a deagglomeration treatment to obtain treated particles a having an average diameter D and high hardness; (4) According to the distance h between the convex points, the configuration ratio of the treated particles a and the dispersed PTFE particles is obtained. After the two particles are mixed and stirred according to the ratio, a partial fiberization treatment is performed. The morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are fiberized under stress to obtain the treated particles b. (5) Placing the treated particles b and the PTFE particles in layers to form an asymmetric membrane by extrusion, calendaring, and stretching; (6) mixing the fluorine-based monomer, the electrostatic conductive material and the alcohol solvent to obtain a prefabricated solution; (7) spraying the prefabricated solution onto the surface of the substrate to obtain a treated substrate; (8) The asymmetric membrane is hot-pressed and laminated onto a treated substrate to form an organic composite material with ultra-high salt resistance.

2. The process for preparing the organic composite material with ultra-high salt resistance according to claim 1, characterized in that: The convex point morphology in the microscopic morphology affecting the surface roughness obtained by computational simulation in step (1) includes circular, elliptical and columnar structures; the convex point spacing h ranges from 0.02 to 195 microns.

3. The process for preparing the organic composite material with ultra-high salt resistance according to claim 1, characterized in that: The average diameter D of step (2) is in the range of 0.01-100 μm.

4. The process for preparing the organic composite material with ultra-high salt resistance according to claim 1, characterized in that: The heat curing treatment methods described in step (3) include high-temperature box heat treatment, high-temperature double-roller hot pressing, and infrared point-to-point radiation heat curing.

5. The process for preparing the organic composite material with ultra-high salt resistance according to claim 1, characterized in that: The curing temperature of the heat curing treatment in step (3) is 120-400°C, and the heat curing treatment time is adjusted accordingly according to different treatment methods.

6. The process for preparing the organic composite material with ultra-high salt resistance according to claim 1, characterized in that: The deagglomeration treatment method described in step (3) includes high-frequency mechanical vibration, ultrasonic vibration, and electromagnetic vibration.

7. The process for preparing the organic composite material with ultra-high salt resistance according to claim 1, characterized in that: The mass ratio of the treated particles a and the PTFE particles in step (4) is 1:50-20:50, and the mixing time is 0.5-10 minutes.

8. The process for preparing the organic composite material with ultra-high salt resistance according to claim 1, characterized in that: The treated particles b described in step (5) are placed on top of the PTFE particles, the treated particles b are distributed in one layer, and the number of PTFE particle layers is two or more.

9. The process for preparing the organic composite material with ultra-high salt resistance according to claim 1, characterized in that: The fluorine-based monomer in step (6) includes one or more of perfluoroacrylate, ethyl perfluoropropionate, methyl perfluoroacetate, perfluoropolyether, perfluorodimethyl ether, and perfluoroalkoxy sulfonic acid; the electrostatic conductive material includes one or more of aluminum nitride, silicon dioxide, and silicon carbide; the mass ratio of the fluorine-based monomer to the alcohol solvent is 0.5:10 to 5:10, and the mass ratio of the electrostatic conductive material to the alcohol solvent is 0.1:10 to 1:

10.

10. The process for preparing the organic composite material with ultra-high salt resistance according to claim 1, characterized in that: The prefabricated solution spraying method described in step (7) includes unidirectional spraying, bidirectional spraying, and electrostatic spraying.

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