CN110787660A - Method for recycling organic-inorganic composite membrane ceramic support - Google Patents
Method for recycling organic-inorganic composite membrane ceramic support Download PDFInfo
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- 238000004064 recycling Methods 0.000 title claims abstract description 11
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 15
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- 239000007788 liquid Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- -1 Polydimethylsiloxane Polymers 0.000 claims description 2
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- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- QQECJQWAJVDVGA-UHFFFAOYSA-N C#CC.[Si] Chemical compound C#CC.[Si] QQECJQWAJVDVGA-UHFFFAOYSA-N 0.000 claims 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for recycling an organic-inorganic composite membrane ceramic support, which comprises the steps of carrying out high-temperature treatment on organic polymer-ceramic composite membrane defective products or organic-inorganic composite membranes damaged after long-term use in an atmosphere, and cleaning residues obtained after calcination of the composite membranes on the surface of the ceramic support and in a pore channel to obtain the recyclable and recyclable high-quality ceramic support. By recoating the organic polymer, an organic-inorganic composite membrane having separation performance is prepared. The method has simple and economic process, realizes the recycling of the high-quality ceramic support body, ensures the stability of the structure of the ceramic support body, improves the repeated utilization rate of the inorganic ceramic support body, reduces the production cost of the organic-inorganic composite membrane, and has universality and good industrial application prospect.
Description
Technical Field
The invention relates to a method for recycling an organic-inorganic composite membrane ceramic support, wherein an organic polymer/ceramic composite membrane prepared by the recycled ceramic support can still be used for pervaporation, gas separation, VOCs separation and the like.
Background
The separation, purification and concentration of substances are important components in the chemical production process, and occupy most of the cost and energy consumption in the total production. Therefore, the development of a high-efficiency and energy-saving separation process has very important strategic significance on the sustainable development of green chemical industry. Compared with the traditional separation technology (such as rectification, extraction, drying and the like), the pervaporation membrane technology is used as an efficient, energy-saving and environment-friendly separation technology and has the characteristics of wide application field and high separation efficiency.
At present, the novel organic polymer/ceramic composite membrane has the intrinsic properties of both organic polymer and inorganic ceramic supports. The membrane has the characteristics of high separation performance, convenient operation, convenient amplification preparation, wide applicability and the like, and is applied to the industries of biological fermentation, recovery of aromatic substances, refining of wine and the like. The high-quality inorganic ceramic support has the advantages of small mass transfer resistance, high mechanical strength, good chemical stability and the like, but has high production cost and technical requirements. Therefore, in order to realize the wide application of the organic polymer/ceramic composite membrane, it is possible to reduce the production cost by sintering the ceramic support by pulverizing and blending the cheaper mineral or the old support, and it is certainly feasible and necessary to recycle the ceramic support of the organic polymer/ceramic composite membrane defective or the organic-inorganic composite membrane broken after long-term use. The preparation method can realize the recycling of the high-quality ceramic support body and create certain commercial value. Not only can reduce the consumption of mineral and chemical resources, but also can avoid the influence of ceramic solid waste on the environment.
Disclosure of Invention
The invention aims to provide a method for recycling an organic-inorganic composite membrane ceramic support. The method is beneficial to recycling of the high-quality ceramic support, and the prepared composite membrane shows good permeation flux, separation selectivity and stability in separation of an alcohol-water system. The recycling and re-preparing method is simple and easy to implement, saves the production cost and is green and environment-friendly.
The technical scheme of the invention is as follows: a method for recycling an organic-inorganic composite membrane ceramic support comprises the following specific steps:
(1) and (3) recovering and treating the organic-inorganic composite membrane ceramic support: placing the defective organic polymer-ceramic composite membrane or the damaged organic polymer-ceramic composite membrane after long-term use in a tubular high-temperature furnace, and calcining under the protection of atmosphere; cooling, then cleaning the ceramic support body, taking out and drying for later use;
(2) reuse of ceramic support: standing the pretreated ceramic support body in a coating liquid, taking out the ceramic support body, and naturally curing the ceramic support body in the air along with the volatile polymer of the solvent to form an organic polymer film layer; and finally, placing the composite membrane in an oven for heating to obtain the organic polymer-ceramic composite membrane.
Preferably, the organic polymer-ceramic composite membrane obtained in the step (2) is composed of an organic separation layer and an inorganic support layer, wherein the organic high-molecular polymer is used as the separation layer, and the high-quality porous inorganic ceramic support is used as the support layer; the thickness of the separation layer is 5-15 μm.
Preferably, the material of the ceramic support is at least one of alumina, zinc oxide, zirconia, titania and mullite.
Preferably, the ceramic support is at least one of a ceramic tube, a ceramic hollow fiber and a ceramic sheet. The ceramic support preferably has a pore diameter of 100 to 350 nm.
Preferably, the atmosphere protection in step (1) is one of inert gases such as nitrogen, helium or argon.
Preferably, the calcination temperature in step (1) is the complete decomposition temperature of the organic polymer; the heating rate is 1-5 ℃/min; the heat preservation time is 4-7 h; the cooling rate is 1-5 ℃/min. Preferably, the cleaning time in the step (1) is 1-2 h.
The pretreated ceramic support in the step (2) is obtained by immersing the ceramic support in pure water to fill the pores of the support.
Preferably, the coating solution in the step (2) is one of Polydimethylsiloxane (PDMS), polyether block amide (PEBA), polytrimethylsilane-1-propyne (PTMSP), polyvinyl alcohol (PVA) and Chitosan (CS); the mass concentration of the coating liquid is 5-15%; the viscosity is 70-150 cP (centipoise) at 25 ℃; the coating time is 30-150 s.
Preferably, the solvent volatilization time in the step (2) is 24-48 h; the temperature of the oven is 50-150 ℃.
Has the advantages that:
the method of the invention recycles and prepares the defective products of the organic polymer/ceramic composite membrane or the ceramic support body of the organic-inorganic composite membrane damaged after long-term use, so that the high-quality ceramic support body can be recycled, and the production cost of raw materials and the consumption of mineral resources are reduced. The ceramic support has the characteristics of high mechanical strength, acid and alkali resistance, no swelling, good thermal stability and the like. The membrane formed by compounding the ceramic support body and the organic polymer can preferentially permeate organic matters, and simultaneously, higher permeation flux, separation selectivity and membrane structure stability are obtained, so that the efficiency of the material separation process is improved. The thickness and the integrity of the film layer are optimized by adjusting the relevant preparation conditions of the film, and the separation performance of the composite film is effectively regulated and controlled so as to adapt to the separation requirements of different systems. The method has simple and economic process and wide application range.
Drawings
FIG. 1 is a scanning electron micrograph of a cross section of a PDMS/ceramic tube composite membrane prepared in example 1. From the electron micrograph, it can be seen that the organic film layer and the inorganic support layer are tightly bonded, have no defects, and the film thickness is about 6.64 μm.
FIG. 2 is a scanning electron micrograph of a cross section of a PEBA/ceramic hollow fiber composite membrane obtained in example 7. From the electron micrograph, it can be seen that the organic film layer and the inorganic support layer are tightly bonded, have no defects, and the film thickness is about 7.51 μm.
Detailed Description
Comparative example 1
Determination of fresh ceramic tubes (pore diameter 250nm and transition layer of ZrO)2) The PDMS/ceramic composite membrane prepared by the support has the separation performance on a 5 wt% ethanol/water system at 40 ℃, and the permeation flux of the membrane is 1.4kg/m2h, separation factor 8.0. For a separation performance of a 1 wt% butanol/water system at 40 ℃, the permeation flux of the membrane was 1.2kg/m2h, separation factor 23.
Comparative example 2
Determination of fresh single-channel ceramic hollow fiber (aperture 100nm, material is Al)2O3) The PEBA/ceramic hollow fiber composite membrane prepared by the support has the separation performance on a 5 wt% ethanol/water system at 40 ℃, and the permeation flux of the membrane is 1.9kg/m2h, separation factor 8.6. For a separation performance of a 1 wt% butanol/water system at 60 ℃, the permeation flux of the membrane was 4.0kg/m2h, separation factor 21.
Comparative example 3
Determination of fresh single-channel ceramic hollow fiber (aperture 100nm, material is Al)2O3) The PVA/ceramic hollow fiber composite membrane prepared by the support has the separation performance on a 90 wt% ethanol/water system at the temperature of 60 ℃, and the permeation flux of the membrane is 0.5kg/m2h, separation factor 1500. For a separation performance of an 8 wt% ethyl acetate/water system at 50 ℃, the permeation flux of the membrane was 2.2kg/m2h, separation factor 550.
Example 1
(1) PDMS/ceramic tube (aperture 250nm and transition layer ZrO)2) And placing the composite membrane in a tubular high-temperature furnace, and calcining under the protection of nitrogen atmosphere. Heating from room temperature to 900 ℃, wherein the heating rate is 2 ℃/min; the heat preservation time is 5 hours; then cooling to room temperature at a cooling rate of 4 ℃/min. And (3) placing the ceramic support body subjected to calcination treatment in an ultrasonic device with the power of 100W for cleaning for 1h, taking out, and drying at 100 ℃ for later use.
(2) And coating the PDMS coating liquid with the viscosity of 120cP and the weight percent of 8 at the temperature of 25 ℃ on the recovered and cleaned ceramic tube support for 80 s. Taking out and naturally curing in air for 24 h. Drying at 100 ℃ to obtain the composite membrane.
The scanning electron micrograph of the cross section of the prepared PDMS/ceramic tube composite membrane is shown in figure 1, and from the electron micrograph, it can be seen that the organic membrane layer and the inorganic support layer are tightly combined without defects, and the thickness of the membrane layer is about 6.64 μm.
The separation performance of the composite membrane prepared in this example was measured for a 5 wt% ethanol/water system at 40 deg.C, and the permeation flux of the membrane was 1.3kg/m2h, separation factor 8.1.
Example 2
(1) PDMS/ceramic plate (aperture 300nm, material ZnO)2) And placing the composite membrane in a tubular high-temperature furnace, and calcining under the protection of argon atmosphere. Heating from room temperature to 900 ℃, wherein the heating rate is 2 ℃/min; the heat preservation time is 6 h; then cooling to room temperature at a cooling rate of 2 ℃/min. And (3) placing the ceramic support body subjected to atmosphere calcination treatment in an ultrasonic device with the power of 100W for cleaning for 1h, taking out, and drying at 100 ℃ for later use.
(2) Coating PDMS coating solution with viscosity of 100cP and 10 wt% at 25 ℃ to recovered and cleaned ZnO2The coating time on the ceramic sheet was 50 s. Taking out and naturally curing in air for 24 h. Drying at 70 ℃ to obtain the composite membrane. The thickness of the film layer was about 6.5 μm.
The separation performance of the composite membrane prepared in this example was measured for a 5 wt% ethanol/water system at 40 ℃ and the permeation flux of the membrane was 1.1kg/m2h, separation factor 8.5.
Example 3
(1) PDMS/ceramic hollow fiber (aperture 100nm, material is Al)2O3) And placing the composite membrane in a tubular high-temperature furnace, and calcining under the protection of nitrogen atmosphere. Heating from room temperature to 900 ℃, wherein the heating rate is 2 ℃/min; the heat preservation time is 6 h; then cooling to room temperature at a cooling rate of 2 ℃/min. And (3) placing the ceramic support body subjected to atmosphere calcination treatment in an ultrasonic device with the power of 100W for cleaning for 2h, taking out, and drying at 100 ℃ for later use.
(2) Coating PDMS coating liquid with the viscosity of 80cP and the weight percent of 10 at the temperature of 25 ℃ to the recovered and cleaned Al2O3The coating time on the hollow fibers was 70 s. Taking out and naturally curing in air for 24 h. Drying at 100 ℃ to obtain the composite membrane. The thickness of the film layer is about 5.5 μm.
The composite film prepared in this example was tested for 40 deg.CSeparation Performance of 1 wt% butanol/water System, permeation flux of Membrane 1.3kg/m2h, separation factor 35.
Example 4
(1) PEBA/ceramic hollow fiber (aperture of 100nm, material of Al)2O3) And placing the composite membrane in a tubular high-temperature furnace, and calcining under the protection of helium atmosphere. Heating from room temperature to 700 ℃, wherein the heating rate is 1 ℃/min; the heat preservation time is 5 hours; then cooling to room temperature at a cooling rate of 1 ℃/min. And (3) placing the ceramic support body subjected to atmosphere calcination treatment in an ultrasonic device with the power of 100W for cleaning for 2h, taking out, and drying at 100 ℃ for later use.
(2) Coating 6 wt% PEBA coating solution with viscosity of 80cP at 25 ℃ to recovered and cleaned Al2O3The coating time on the hollow fiber was 100 s. Taking out and naturally curing in air for 24 h. Drying at 70 ℃ to obtain the composite membrane. The thickness of the film layer is about 10 μm.
The separation performance of the composite membrane prepared in this example was measured for a 5 wt% ethanol/water system at 40 deg.C, and the permeation flux of the membrane was 1.8kg/m2h, separation factor 8.8.
Example 5
(1) PVA/ceramic hollow fiber (with pore diameter of 200nm and TiO material)2) And placing the composite membrane in a tubular high-temperature furnace, and calcining under the protection of atmosphere. The temperature is raised from room temperature to 700 ℃, and the heating rate is 1 ℃/min; the heat preservation time is 5 hours; then cooling to room temperature at a cooling rate of 2 ℃/min. And (3) cleaning the ceramic support body subjected to atmosphere calcination treatment in an ultrasonic device with the power of 100W for 1.5h, taking out, and drying at 100 ℃ for later use.
(2) Coating 7 wt% PVA coating liquid with viscosity of 100cP at 25 ℃ on recovered and cleaned TiO2The coating time on the hollow fibers was 90 s. Taking out and naturally curing in air for 24 h. Drying at 60 ℃ to obtain the composite membrane. The thickness of the film layer is about 6 μm.
The separation performance of the composite membrane prepared in this example was measured for a system of 8 wt% ethyl acetate/water at 50 ℃ and the permeation flux of the membrane was 2.1kg/m2h, separation factor 500.
Example 6
(1) Placing the PDMS/ceramic hollow fiber (the aperture is 150nm, and the material is mullite) composite membrane in a tubular high-temperature furnace, and calcining under the protection of nitrogen atmosphere. Heating from room temperature to 900 ℃, wherein the heating rate is 2 ℃/min; the heat preservation time is 6 h; then cooling to room temperature at a cooling rate of 2 ℃/min. And (3) placing the ceramic support body subjected to atmosphere calcination treatment in an ultrasonic device with the power of 100W for cleaning for 2h, taking out, and drying at 100 ℃ for later use.
(2) Coating a PDMS coating solution with the viscosity of 80cP and the weight percent of 10 at the temperature of 25 ℃ on the recycled and cleaned mullite hollow fiber with the aperture of 100nm, wherein the coating time is 100 s. Taking out and naturally curing in air for 24 h. Drying at 100 ℃ to obtain the composite membrane. The thickness of the film layer is about 13 μm.
The separation performance of the composite membrane prepared in this example was measured for a 1 wt% butanol/water system at 40 deg.C, and the permeation flux of the membrane was 1.3kg/m2h, separation factor 35.
Example 7
(1) PTMSP/ceramic tube (aperture 250nm and transition layer ZrO)2) And placing the composite membrane in a tubular high-temperature furnace, and calcining under the protection of helium atmosphere. Heating from room temperature to 750 deg.c at the rate of 5 deg.c/min; the heat preservation time is 6 h; then cooling to room temperature at a cooling rate of 5 ℃/min. And (3) placing the ceramic support body subjected to atmosphere calcination treatment in an ultrasonic device with the power of 100W for cleaning for 1h, taking out, and drying at 100 ℃ for later use.
(2) Coating the PTMSP coating solution with the viscosity of 130cP and the concentration of 12 wt% at 25 ℃ on a recovered and cleaned ceramic tube support for 90 s. Taking out and naturally curing in air for 24 h. Drying at 80 ℃ to obtain the composite membrane.
The scanning electron micrograph of the cross section of the resulting PEBA/ceramic hollow fiber composite membrane is shown in FIG. 2. From the electron micrograph, it can be seen that the organic film layer and the inorganic support layer are tightly bonded, have no defects, and the film thickness is about 7.51 μm.
The separation performance of the composite membrane prepared in this example was measured for a 1 wt% butanol/water system at 70 ℃, and the permeation flux of the membrane was 1.0kg/m2h, separation factor 70.
Example 8
(1) Placing CS/ceramic tube (aperture is 100nm, material is ZrO)2) And placing the composite membrane in a tubular high-temperature furnace, and calcining under the protection of helium atmosphere. Heating from room temperature to 600 deg.C at a heating rate of 2 deg.C/min; the heat preservation time is 6 h; then the temperature is reduced to the room temperature, and the temperature reduction rate is 3 ℃/min. And (3) placing the ceramic support body subjected to atmosphere calcination treatment in an ultrasonic device with the power of 100W for cleaning for 1h, taking out, and drying at 100 ℃ for later use.
(2) Coating a CS coating solution with the viscosity of 80cP and the weight percent of 5 at the temperature of 25 ℃ to the recycled and cleaned ZrO2The coating time on the hollow fiber was 120 s. Taking out and naturally curing in air for 36 h. Drying at 50 ℃ to obtain the composite membrane. The thickness of the film layer is about 6 μm.
The separation performance of the composite membrane prepared in this example was measured for a 90 wt% ethanol/water system at 60 deg.C, and the permeation flux of the membrane was 0.5kg/m2h, separation factor 2000.
Claims (10)
1. A method for recycling an organic-inorganic composite membrane ceramic support comprises the following specific steps:
(1) and (3) recovering and treating the organic-inorganic composite membrane ceramic support: placing the defective organic polymer-ceramic composite membrane or the damaged organic polymer-ceramic composite membrane after long-term use in a tubular high-temperature furnace, calcining under the protection of atmosphere, cooling, cleaning the ceramic support body, taking out and drying for later use;
(2) reuse of ceramic support: standing the pretreated ceramic support body in a coating liquid, taking out the ceramic support body, and naturally curing the ceramic support body in the air along with the volatile polymer of the solvent to form an organic polymer film layer; and finally, placing the composite membrane in an oven for heating to obtain the organic polymer-ceramic composite membrane.
2. The method of claim 1, wherein: the organic polymer-ceramic composite membrane obtained in the step (2) is composed of an organic separation layer and an inorganic support layer, wherein the organic high-molecular polymer is used as the separation layer, and the high-quality porous inorganic ceramic support body is used as the support layer; the thickness of the separation layer is 5-15 μm.
3. The method of claim 1, wherein: the ceramic support body is made of at least one of alumina, zinc oxide, zirconia, titanium oxide or mullite.
4. The method of claim 1, wherein: the ceramic support body is at least one of a ceramic tube, a ceramic hollow fiber and a ceramic sheet.
5. The method of claim 1, wherein: the aperture of the ceramic support is 100-350 nm.
6. The method of claim 1, wherein: the atmosphere protection in the step (1) is one of nitrogen, helium or argon.
7. The method of claim 1, wherein: the calcination temperature in the step (1) is the complete decomposition temperature of the organic polymer; the heating rate is 1-5 ℃/min; the heat preservation time is 4-7 h; the cooling rate is 1-5 ℃/min.
8. The method of claim 1, wherein: the cleaning time in the step (1) is 1-2 h.
9. The method according to claim 1, wherein the coating solution in the step (2) is one of Polydimethylsiloxane (PDMS), polyether block amide (PEBA), polytrimethyl silicon-1-propyne (PTMSP), polyvinyl alcohol (PVA), and Chitosan (CS); the mass concentration of the coating liquid is 5-15%; the viscosity is 70-150 cP at 25 ℃; the coating time is 30-150 s.
10. The method according to claim 1, wherein the solvent volatilization time in the step (2) is 24 to 48 hours; the temperature of the oven is 50-150 ℃.
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| CN113926320A (en) * | 2021-09-09 | 2022-01-14 | 浙江浙能天然气运行有限公司 | Hollow fiber ceramic composite membrane for VOCs recovery and preparation process thereof |
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