Preparation process of organic composite material with super-high salt resistance

Abstract

The application discloses a preparation process of an organic composite material with super-high salt resistance. The process comprises the following steps: obtaining the convex point shape and the convex point interval h in the micro-morphology of the film through calculation simulation; calculating the average diameter D of the convex point particles; performing heat curing treatment and de-agglomeration treatment on the dispersed polytetrafluoroethylene particles to obtain treated particles a; according to the h between the convex points, the configuration ratio of the treated particles a and the dispersed PTFE particles is obtained, the particles are mixed and stirred according to the ratio, and then fiberization treatment is performed to obtain treated particles b; the two kinds of particles are placed in layers, and an asymmetric film is formed through a stretching process; a fluorine monomer, an electrostatic conductive material and an alcohol solvent are mixed to obtain a prepared solution; the prepared solution is sprayed on the surface of a base material to obtain a treated base material; and the asymmetric film is hot-pressed and laminated on the base material to form the organic composite material. The film material is suitable for a flue gas filtration system in different industries, and is especially suitable for the purification of a medium-low temperature flue gas system with high salting-out degree.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of new functional material preparation, and particularly relates to a preparation process of an organic composite material with super-high salt resistance. BACKGROUND

[0002] In the process of steel smelting, coal-fired power generation and chemical reaction in metallurgy, power and chemical industries, a large amount of acid gas is generated in the flue dust waste gas. The acid gas in the flue dust waste gas is first neutralized by ammonia water, and then the neutralized flue dust waste gas is subjected to heat exchange, dust removal and other operations, and finally discharged into the atmosphere. However, the flue dust waste gas after acid-base neutralization contains ammonia gas composition, and when the temperature of the flue dust waste gas fluctuates, ammonium salt crystals are easily formed. At the same time, a part of the ammonium salt will melt into water vapor to form sticky acidic liquid, which is easy to adhere to the inner surface of the low-temperature section heat exchange equipment, dust removal equipment and the outer surface of the filter material. The crystallization and adhesion of the ammonium salt easily lead to an increase in the running resistance, and the dust removal equipment needs to be cleaned regularly, but this also increases the cost of tail gas treatment, and in addition, the waste water generated by cleaning forms secondary pollution. SUMMARY

[0003] The present application relates to the field of new functional material preparation, and particularly relates to a preparation process of an organic composite material with super-high salt resistance.

[0004] The technical scheme of the present application is as follows:

[0005] A preparation process of an organic composite material with super-high salt resistance, the process steps are as follows:

[0006] (1) The convex point shape and the convex point spacing h in the micro-morphology affecting the surface roughness are obtained by calculation simulation; (2) according to the convex point shape, the average diameter D of the convex point particles is calculated;

[0007] (3) The dispersed polytetrafluoroethylene (PTFE) particles are subjected to heat curing treatment and deagglomeration treatment to obtain high-hardness treated particles a with an average diameter D;

[0008] (4) According to the h between the convex points, the configuration ratio of the treated particles a and the dispersed PTFE particles is obtained, and the two are mixed and stirred according to the ratio, and then subjected to partial fiberization treatment, the shape of the treated particles a remains unchanged, and the dispersed PTFE particles are subjected to stress fiberization to obtain treated particles b;

[0009] (5) The treated particles b and the PTFE particles are placed in layers, and an asymmetric film is formed by pushing, calendering and stretching;

[0010] (6) A pre-prepared solution is obtained by mixing a fluorine-based monomer, an electrostatic conductive material and an alcohol solvent.

[0011] (7) spraying the pre-prepared solution on the surface of the substrate to obtain a treated substrate;

[0012] (8) hot pressing the asymmetric film onto the treated substrate to form an organic composite material with super-high salt resistance. Wherein:

[0013] In step (1), the micro-morphology affecting the surface roughness is obtained by calculation simulation, including round, oval and columnar structures. The distance between the convex points h is in the range of 0.02-195 microns.

[0014] In step (2), according to the convex point morphology, the average diameter D of the convex point particles is calculated, which is in the range of 0.01-100 microns.

[0015] In step (3), the heat curing treatment mode includes but is not limited to high temperature box heat treatment, high temperature double roller hot pressing, infrared point-to-point radiation heat curing, etc.

[0016] In step (3), the curing temperature of the heat curing treatment is 120-400℃.

[0017] In step (3), the de-agglomeration treatment mode includes but is not limited to high-frequency mechanical oscillation, ultrasonic oscillation, electromagnetic oscillation, etc.

[0018] In step (4), the weight ratio of the treated particles a and PTFE particles is 1:50~20:50, and the mixing time is 0.5-10 minutes.

[0019] In step (5), the treated particles b are placed on the PTFE particles, and the treated particles b are distributed in one layer, and the number of layers of PTFE particles is two or more.

[0020] In step (6), the fluorine-based monomer includes but is not limited to one or more of perfluorinated propenoate, perfluorinated propionic acid ethyl ester, perfluorinated methyl acetate, perfluorinated polyether, perfluorinated dimethyl ether, and perfluorinated alkoxy sulfonic acid.

[0021] In step (6), the electrostatic conductive material includes but is not limited to one or more of aluminum nitride, silicon dioxide, and silicon carbide.

[0022] In step (6), the mixing ratio of the fluorine-based monomer and the alcohol solvent is between 0.5:10 and 5:10.

[0023] The mixing ratio of the semiconductor material and the alcohol solvent is between 0.1:10 and 1:10.

[0024] In step (7), the pre-prepared solution spraying mode includes but is not limited to one-way spraying, two-way spraying, electrostatic spraying, etc.

[0025] The beneficial effects of the present application are:

[0026] 1、The organic composite film prepared by the present application has excellent properties such as super-high salt resistance, high separation precision, and large gas flux, and is suitable for flue gas filtration systems in different industries, especially for the purification of medium and low temperature flue gas systems with high degree of salting-out.

[0027] 2、The preparation process of the present application is simple, easy to operate, and convenient for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 The electron microscope image of the asymmetric film of Example 6.

[0029] Figure 2 The electron microscope image of the pre-prepared solution sprayed on the substrate in Example 6.

[0030] Figure 3 The electron microscope image of the organic composite material prepared in Example 6. DETAILED DESCRIPTION

[0031] The present application will be further explained in conjunction with the examples below, which are only used to illustrate the present application, but not to limit the scope of the present application. Example 1

[0032] Through calculation simulation, it is obtained that the convex point shape in the micro-morphology affecting the surface roughness is elliptical, and the convex point spacing h is 195 microns, and the average diameter D of the convex point particles is calculated to be 100 microns.

[0033] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to infrared point-to-point radiation heat curing, and the curing temperature is 200°C, and then the treated particles a with an average diameter D of 100 microns are obtained by high-frequency mechanical oscillation treatment; the treated particles a and the dispersed PTFE particles are mixed and stirred according to a mass ratio of 1:50 for 10 minutes, and then subjected to partial fiberization treatment, the treated particles a remain unchanged, and the dispersed PTFE particles are subjected to fiberization under stress, to obtain treated particles b; the treated particles b and the dispersed PTFE particles are placed in layers, one layer of treated particles b and two layers of PTFE particles, and an asymmetric film is formed by pushing, calendering and stretching.

[0034] The perfluoropropionic acid ethyl ester monomer, aluminum nitride and ethanol are mixed according to a mass ratio of 0.5:0.1:10 to obtain a pre-prepared solution; the pre-prepared solution is attached to the surface of the substrate by a one-way spraying process to obtain a treated substrate.

[0035] The asymmetric film is laminated on the treated substrate to form an organic composite material 1 with super-high salt resistance. Example 2

[0036] The calculation simulation shows that the convex shape in the micro-morphology affecting the surface roughness is elliptical, and the convex spacing h is 10 microns, and the calculation shows that the average diameter D of the convex particles is 15 microns.

[0037] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to infrared point-to-point radiation heat curing at a curing temperature of 200°C, and then subjected to high-frequency mechanical oscillation treatment to obtain treated particles a with an average diameter D of 15 microns; the treated particles a and the dispersed PTFE particles are mixed and stirred at a mass ratio of 10:50 for 2 minutes, and then subjected to partial fiberization treatment, the morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are subjected to fiberization under stress to obtain treated particles b; the treated particles b and the dispersed PTFE particles are placed in layers, one layer of treated particles b and four layers of PTFE particles, and an asymmetric film is formed by pushing, calendering and stretching.

[0038] The perfluoroethyl propionate monomer, aluminum nitride and isopropyl alcohol are mixed at a mass ratio of 1:0.5:10 to obtain a pre-prepared solution; the pre-prepared solution is attached to the surface of the substrate by a one-way spraying process to obtain a treated substrate.

[0039] The asymmetric film is laminated on the treated substrate to form an organic composite material 2 with super-high salt resistance. Example 3

[0040] The calculation simulation shows that the convex shape in the micro-morphology affecting the surface roughness is elliptical, and the convex spacing h is 1 micron, and the calculation shows that the average diameter D of the convex particles is 1.3 microns.

[0041] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to high-temperature box heat curing at a curing temperature of 120°C, and then subjected to ultrasonic oscillation treatment to obtain treated particles a with an average diameter D of 1.3 microns; the treated particles a and the dispersed PTFE particles are mixed and stirred at a mass ratio of 20:50 for 0.5 minutes, and then subjected to partial fiberization treatment, the morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are subjected to fiberization under stress to obtain treated particles b; the treated particles b and the dispersed PTFE particles are placed in layers, one layer of treated particles b and two layers of PTFE particles, and an asymmetric film is formed by pushing, calendering and stretching.

[0042] The perfluoroethyl propionate monomer, aluminum nitride and isopropyl alcohol are mixed at a mass ratio of 1:0.5:10 to obtain a pre-prepared solution; the pre-prepared solution is attached to the surface of the substrate by a one-way spraying process to obtain a treated substrate.

[0043] The asymmetric film is laminated on the treated substrate to form an organic composite material 2 with super-high salt resistance. Example 4

[0044] The calculation simulation shows that the convex shape in the micro-morphology affecting the surface roughness is elliptical, and the convex spacing h is 0.5 microns, and the calculation shows that the average diameter D of the convex particles is 1 micron.

[0045] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to high-temperature box heat treatment, and the curing temperature is 400°C. Then, the particles are treated by ultrasonic oscillation to obtain treated particles a. The treated particles a with an average diameter D of 1 micron and the dispersed PTFE particles are mixed in a mass ratio of 10:50 and stirred for 5 minutes, and then subjected to partial fiberization treatment. The morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are subjected to fiberization under stress 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. An asymmetric membrane is formed by pushing, calendering and stretching.

[0046] The perfluoropropionic acid ethyl ester monomer, silicon dioxide and isopropyl alcohol are mixed in a mass ratio of 0.5:0.1:10 to obtain a pre-prepared solution. The pre-prepared solution is attached to the surface of the substrate by a one-way spraying process to obtain a treated substrate.

[0047] The asymmetric membrane is laminated on the treated substrate to form an organic composite material 4 with super-high salt resistance. Example 5

[0048] The calculation simulation shows that the convex shape in the micro-morphology affecting the surface roughness is elliptical, and the convex spacing h is 0.1 microns, and the calculation shows that the average diameter D of the convex particles is 0.15 microns.

[0049] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to high-temperature double-roller heat pressing and heat curing, and the curing temperature is 300°C. Then, the particles are treated by electromagnetic oscillation to obtain treated particles a with an average diameter D of 0.15 microns. The treated particles a and the dispersed PTFE particles are mixed in a mass ratio of 5:50 and stirred for 5 minutes, and then subjected to partial fiberization treatment. The morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are subjected to fiberization under stress 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. An asymmetric membrane is formed by pushing, calendering and stretching.

[0050] The perfluoropolyether monomer, silicon carbide and ethanol are mixed in a mass ratio of 1:0.5:10 to obtain a pre-prepared solution. The pre-prepared solution is attached to the surface of the substrate by a one-way spraying process to obtain a treated substrate.

[0051] The asymmetric membrane is laminated on the treated substrate to form an organic composite material 5 with super-high salt resistance. Example 6

[0052] The simulation shows that the convex shape in the micro-morphology affecting the surface roughness is elliptical, and the convex spacing h is 0.02 microns, and the average diameter D of the convex particles is calculated to be 0.01 microns.

[0053] The dispersed polytetrafluoroethylene (PTFE) particles are subjected to high-temperature double-roller 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 microns; the treated particles a and the dispersed PTFE particles are mixed and stirred at a mass ratio of 15:50 for 5 minutes, and then subjected to partial fiberization treatment, the morphology of the treated particles a remains unchanged, and the dispersed PTFE particles are subjected to fiberization under stress to obtain treated particles b; the treated particles b and the dispersed PTFE particles are layered and placed, one layer of treated particles b and four layers of PTFE particles, and an asymmetric membrane is formed by pushing, calendering and stretching.

[0054] The perfluorodimethyl ether monomer, aluminum nitride and isopropyl alcohol are mixed at a mass ratio of 3:0.5:10 to obtain a pre-prepared solution; the pre-prepared solution is attached to the surface of the substrate by a one-way spraying process to obtain a treated substrate.

[0055] The asymmetric membrane is laminated on the treated substrate to form an organic composite material 6 with super-high salt resistance.

[0056] The organic composite material with super-high salt resistance prepared in the above examples is subjected to a 96h continuous spraying salt spray test in a 5% sodium chloride neutral solution, and the performance test data of the membrane material before and after the salt spray test are as shown in Table 1.

[0057] According to the calculation, the air permeability of the above organic composite membrane material after the salt spray test decreases by less than 10%, and the filtration resistance increases by less than 15%. Compared with the blank sample, the air permeability decreases by 33%, and the filtration resistance increases by 36%. The organic composite material prepared in the example has obvious salt resistance and can ensure that the membrane material continuously has high air permeability.

[0058] Table 1 Performance test of organic composite material with super-high salt resistance

[0059]

Claims

1. A process for the preparation of an organic composite material with ultra-high salt resistance, characterized in that, The preparation steps are as follows: (1) The convex shape and convex spacing h of the microtopography affecting the surface roughness are obtained by calculation simulation; (2) According to the convex shape, the average diameter D of the convex point particles is calculated; (3) The dispersed polytetrafluoroethylene (PTFE) particles are subjected to heat curing treatment and deagglomeration treatment to obtain high-hardness treated particles a with an average diameter D; the deagglomeration treatment includes high-frequency mechanical oscillation, ultrasonic oscillation or electromagnetic oscillation; (4) According to the convex spacing h, the configuration ratio of the treated particles a and the dispersed PTFE particles is obtained, and the two are mixed and stirred according to the ratio, then subjected to partial fiberization treatment, the treated particles a remain unchanged, and the dispersed PTFE particles are fiberized under stress to obtain treated particles b; (5) The treated particles b and PTFE particles are placed in layers, and an asymmetric film is formed by pushing, calendering and stretching; (6) A pre-prepared solution is obtained by mixing a fluorine-based monomer, an electrostatic conductive material and an alcohol solvent; the fluorine-based monomer includes one or more of perfluoropropenoate, perfluoropropyl acetate, perfluoromethyl acetate, perfluoropolyether, perfluorodimethyl ether and perfluoroalkoxy sulfonic acid; (7) The pre-prepared solution is sprayed on the surface of the substrate to obtain a treated substrate; (8) The asymmetric film is hot-pressed and laminated on the treated substrate to form an organic composite material with super-high salt resistance.

2. The process for the preparation of organic composite materials with super-high salt resistance according to claim 1, characterized in that, The convex shape of the microtopography affecting the surface roughness obtained by calculation simulation in step (1) includes circular, elliptical and columnar structures; the convex spacing h is in the range of 0.02-195 microns.

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

4. The process for preparing the organic composite material having super-high salt resistance according to claim 1, characterized in that, The heat curing treatment in step (3) includes 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 having super-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 the different treatment methods.

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

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

8. The process for preparing an organic composite material having super-high salt resistance according to claim 1, characterized in that, The electrostatic conductive material in step (6) 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 0.5:10~5:10, and the mass ratio of the electrostatic conductive material to the alcohol solvent is 0.1:10~1:

10.

9. The process for preparing the organic composite material having super-high salt resistance according to claim 1, characterized in that, The pre-prepared solution spraying method in step (7) includes one-way spraying, two-way spraying and electrostatic spraying.

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