CN114849476A - Pervaporation membrane and preparation method, assembly and application thereof - Google Patents
Pervaporation membrane and preparation method, assembly and application thereof Download PDFInfo
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- CN114849476A CN114849476A CN202210603076.8A CN202210603076A CN114849476A CN 114849476 A CN114849476 A CN 114849476A CN 202210603076 A CN202210603076 A CN 202210603076A CN 114849476 A CN114849476 A CN 114849476A
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- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
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- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
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- B01D71/06—Organic material
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- B01D71/34—Polyvinylidene fluoride
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Abstract
The invention discloses a pervaporation membrane and a preparation method, a component and application thereof. The preparation method of the pervaporation membrane comprises the following steps: (1) reacting the raw material mixture to obtain a membrane building liquid; the raw material mixture comprises a polymer and a cross-linking agentCatalysts, solvents, photocatalysts; the mass ratio of the polymer to the photocatalyst is 10 (0.05-0.6); the photocatalyst comprises TiO 2 And/or modified TiO 2 (ii) a (2) And preparing the membrane building liquid into a liquid membrane, and curing to obtain the pervaporation membrane. The invention combines photocatalysis and permeable membrane technology and carries TiO 2 After each batch of wastewater treatment is finished, the ultraviolet lamp is turned on to carry out photocatalytic reaction, and organic pollutants adsorbed on the surface of the membrane are removed, so that the membrane pollution is slowed down, and the service life of the membrane is prolonged. The permeation flux retention rate of 8 runs can be more than 81%, and the permeation flux retention rate of 16 runs can be more than 71%.
Description
Technical Field
The invention particularly relates to a pervaporation membrane and a preparation method, a component and application thereof.
Background
Pervaporation (PV) membrane separation technology is a new type of membrane separation technology. The technology is used for separating liquid mixture, and has the outstanding advantage of realizing separation tasks which are difficult to be completed by traditional methods such as distillation, extraction, adsorption and the like with low energy consumption. It is especially suitable for the separation of the mixture with near boiling point and constant boiling point which is difficult to separate or can not be separated by common rectification; the removal of trace water in organic solvent and mixed solvent has obvious economic and technical advantages for separating a small amount of organic pollutants in waste water. Pervaporation membrane separation technology is to utilize the difference of solubility (thermodynamic property) and diffusivity (kinetic property) of organic solvent and water (or different components in the solvent) in a dense membrane to make water (or a certain component) permeate the membrane and then vaporize on the other side of the membrane, thereby realizing the separation process. The pervaporation organic matter permeable membrane is adopted to treat high-concentration organic wastewater, so that the energy consumption is low, the cost is low, and the organic matter can be recycled and recycled at the front end of the working procedure.
In the process of treating actual wastewater by using the pervaporation membrane, high-boiling-point organic pollutants are easily adsorbed to the surface of the membrane, but are difficult to desorb from the vacuum side, so that the membrane is polluted after a long time, and the permeation flux is reduced. CN101229491A discloses a preparation method of a pervaporation membrane which is permeable to dimethyl carbonate preferentially, but has no anti-pollution performance; CN10912198A discloses a method for preparing a pervaporation membrane by photocatalysis, which shortens the curing time of the pervaporation membrane and reduces the possibility of the membrane building liquid permeating into a bottom membrane, but has no anti-pollution performance; CN112979890A discloses a method for preparing a fluorine-containing pervaporation membrane, which has a stronger hydrophobic effect than original PDMS, and fluorine can reduce the free energy of the membrane surface and enhance the biological pollution resistance of the membrane, but does not have the pollution resistance to high-boiling point organic matters.
Therefore, it is of great significance to prepare a pervaporation membrane with anti-pollution performance.
Disclosure of Invention
The invention provides a pervaporation membrane and a preparation method, a component and application thereof, aiming at overcoming the problem of membrane pollution of the pervaporation membrane in the prior art. The invention is carried out by loading TiO 2 Particles, reducing the membrane pollution of the pervaporation membrane and prolonging the service life of the membrane.
The core idea of the invention is to combine the photocatalytic and pervaporation membrane technologies, since TiO 2 Under the action of radiation with specific wavelength, photochemical reaction can take place to decompose most organic substances and degrade pollutants, and TiO is introduced into the pervaporation membrane material 2 And the proper operation mode is combined to solve the problem of membrane pollution caused by the application of the pervaporation membrane material to actual wastewater. But TiO 2 2 The defects of easy agglomeration, difficult separation, recovery and recycling and the like exist, and based on the defects, the inventor tries to prepare the TiO 2 The carrier is loaded on the surface of the pervaporation membrane, so that the pervaporation membrane degrades the attached organic pollutants through photocatalytic operation in the process of wastewater treatment, and a better treatment effect can be obtained even if the pervaporation membrane operates for multiple times.
The present invention solves the above technical problems by the following technical solutions.
The invention provides a preparation method of a pervaporation membrane, which comprises the following steps:
(1) reacting the raw material mixture to obtain a membrane building liquid; the raw material mixture comprises a polymer, a cross-linking agent, a catalyst, a solvent and a photocatalyst; the mass ratio of the polymer to the photocatalyst is 10 (0.05-0.6); the photocatalyst comprises TiO 2 And/or modified TiO 2 ；
(2) And preparing the membrane building liquid into a liquid membrane, and curing to obtain the pervaporation membrane.
In the step (1) of the present invention, the modified TiO 2 The TiO can be prepared by conventional methods in the field 2 And (4) modifying.
Wherein the modified TiO is 2 Can be prepared by mixing ordinary TiO 2 Dispersing in ethanol ammonia water solution, performing ultrasonic dispersion, then dropwise adding ethanol solution of silane coupling agent, rapidly stirring for reaction, washing, centrifuging, and drying to obtain modified TiO 2 。
The pH value of the ethanol ammonia water solution can be 8-10, such as 9.
The volume fraction of ethanol in the ethanolic ammonia solution can be 50%.
The ordinary TiO 2 The mass ratio of the ethanol ammonia water solution to the ethanol ammonia water solution can be 1 (5-10), such as 1: 7.
The time of ultrasonic dispersion can be 10-20 min, such as 15 min.
The silane coupling agent may be KH-570, KH560 or KH550, preferably KH570, i.e., gamma-methacryloxypropyltrimethoxysilane.
The volume fraction of the silane coupling agent in the ethanol solution of the silane coupling agent may be 2.5% to 5%, for example 3%.
The dropwise addition can be carried out at 60 to 80 ℃, for example at 70 ℃.
The dropwise addition can be carried out while stirring, and the ethanol solution of the silane coupling agent is added.
The rapid stirring speed can be 800-1000 r/min, such as 900 r/min.
The reaction time can be 3-5 h, for example 4 h.
The reaction time may be 60 to 80 ℃, for example 70 ℃.
The silane coupling agent and TiO 2 The mass ratio of (1) to (2) may be (0.5-2.0): 10, for example, 1: 10.
In step (1) of the present invention, the raw material mixture may be prepared by first stirring the polymer, the crosslinking agent, the solvent and the photocatalyst, and then adding the catalyst.
Wherein the stirring speed can be 800-1000 r/min, such as 900 r/min.
Wherein the stirring time can be 3-5 h, such as 4 h.
In the step (1), the reaction time may be 15-30 min, for example, 20 min.
In step (1) of the present invention, the casting solution is generally subjected to defoaming treatment.
The defoaming treatment method can be standing for 0.5-1 h, such as 0.6 h.
In step (1) of the present invention, the polymer is a crosslinkable polymer conventionally used in the art for producing a pervaporation membrane.
Wherein the polymer may be one or more of a silicon-containing polymer, a fluoropolymer, a polysubstituted alkyne, a block polyether polyamide, and a methacrylate-styrene polymer.
The silicon-containing polymer can be polydimethylsiloxane or polytrimethyl-silylpropyne; the polydimethylsilane can be a hydroxyl terminated polydimethylsiloxane or a vinyl terminated polydimethylsiloxane.
The fluoropolymer may be polytetrafluoroethylene or polyvinylidene fluoride.
In step (1) of the present invention, the crosslinking agent is used to crosslink the polymer, and the kind of the crosslinking agent may be selected according to the kind of the polymer.
Wherein, when the polymer is hydroxyl-terminated polydimethylsiloxane, the cross-linking agent can be one or more of Tetraethoxysilane (TEOS), methyltrimethoxysilane, vinyltriethoxysilane or other polyoxysilanes;
wherein, when the polymer is a vinyl terminated polydimethylsiloxane, the cross-linking agent can be a polysiloxane containing a hydrosil group.
In step (1) of the present invention, the catalyst is used for catalyzing the polymer reaction, and the kind of the catalyst can be selected according to the kind of the polymer.
Wherein, when the polymer is a hydroxyl-terminated polydimethylsiloxane, the catalyst can be an organotin catalyst, preferably dibutyltin dilaurate (TBDTL);
wherein, when the polymer is vinyl terminated polydimethylsiloxane, the catalyst can be an organo-platinum catalyst, preferably Karstedt's catalyst.
In step (1) of the present invention, the solvent may be a volatile solvent which is conventional in the art, and is capable of dissolving the polymer and not participating in the polymerization reaction.
Wherein the solvent can be n-heptane, toluene, n-hexane, isopropanol, and dichloromethane.
In the step (1) of the present invention, the mass ratio of the polymer to the photocatalyst may be 10 (0.1-0.5), preferably 10 (0.2-0.4), for example 10: 0.3.
In step (1) of the present invention, the mass ratio of the polymer to the solvent may be 10 (20-50), preferably 10 (30-40), for example 10: 35.
In the step (1) of the present invention, the mass ratio of the polymer to the catalyst may be 10 (0.3 to 0.5), for example, 10: 0.4.
In the step (1) of the present invention, the mass ratio of the photocatalyst to the solvent may be (0.001 to 0.03):1, preferably (0.002 to 0.025):1, for example, 0.004: 1.
In the step (1) of the present invention, the mass ratio of the polymer to the crosslinking agent may be 10 (0.75 to 1.25), for example, 10: 1.
In step (1) of the present invention, the mass ratio of the polymer, the crosslinking agent, the catalyst, the solvent, and the photocatalyst may be 10:1: (0.3-0.5): (20-50): (0.05-0.6), for example, 10:1:0.5:50:0.1, 10:1:0.5:50:0.2 or 10:1:0.5:50: 0.5.
In the step (1) of the invention, the viscosity of the casting solution can be 30-50 mpa · s, for example 40mpa · s.
In the step (2), the liquid membrane is prepared by coating the membrane-forming solution on the PVDF ultrafiltration membrane.
In the step (2), the thickness of the liquid film may be 25-150 μm.
In step (2) of the present invention, the curing comprises standing and drying.
Wherein the standing time can be 1-2 hours.
Wherein, the temperature of the standing can be room temperature.
Wherein the drying may be performed in an oven.
Wherein the drying temperature can be 60-100 ℃, for example, 70 ℃.
Wherein, the drying time can be 6-10 hours, such as 8 hours.
In the invention, the room temperature is 20-30 ℃.
In step (2) of the present invention, a crosslinking reaction occurs during the curing process.
The invention also provides a pervaporation membrane prepared by the preparation method.
The invention also provides a pervaporation membrane module which comprises the pervaporation membrane.
The prepared supported TiO 2 The PDMS/PVDF pervaporation membrane is welded on an ABS support flat plate in a hot melting mode to form the membrane element. The support both sides plane of flat board all lay sharp runner at interval, through the water conservancy diversion cloth of hot melt welding PET non-woven fabrics material on the sharp runner plane, sharp runner is connected with the vacuum bleeder vent, the backup pad top is equipped with the installation handle.
And a plurality of membrane elements are assembled on the bracket in a parallel arrangement mode, and the vacuum pumping ports of the pervaporation flat membrane elements are connected into a whole by a main gas collecting pipe to form a top vacuum pumping hole of the pervaporation membrane module. The middle of each line of membrane elements is provided with 1 ultraviolet lamp tube.
The invention also provides application of the pervaporation membrane in the field of water treatment.
Will be made into a negativeLoaded with TiO 2 The PDMS/PVDF pervaporation membrane module is placed in a raw material pool, the water-based paint waste liquid of the automobile factory after coagulation treatment is heated to 55-65 ℃, and then the water-based paint waste liquid is pumped into the raw material pool. The raw material pool is circulated by a pump, so that the concentration polarization on the surface of the pervaporation membrane is avoided. The vacuum pumping hole at the top of the pervaporation membrane module is connected with a condenser and a vacuum pump, and the pumped organic gas is condensed.
The pervaporation operation process parameters are that the feeding temperature is 55-65 ℃, the vacuum degree of a gas phase side is 500-2000 Pa, and the condensation temperature of penetrating fluid is-10-0 ℃. After each batch of wastewater is treated by pervaporation wastewater, the ultraviolet lamp is turned on to remove organic pollutants which are adsorbed on the surface of the pervaporation membrane but not desorbed through photocatalytic reaction, so that membrane pollution is reduced, and the service life of the membrane is prolonged.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the invention combines photocatalysis and permeable membrane technology and carries TiO 2 After each batch of wastewater treatment is finished, the ultraviolet lamp is turned on to carry out photocatalytic reaction, and organic pollutants adsorbed on the surface of the membrane are removed, so that the membrane pollution is slowed down, and the service life of the membrane is prolonged. The permeation flux retention rate of 8 runs can be more than 81%, and the permeation flux retention rate of 16 runs can be more than 71%.
In a preferred embodiment, the permeate flux after 8 batches of wastewater run may be more than 96% of the initial permeate flux, and the permeate flux after 8 batches of wastewater run may be more than 92% of the initial permeate flux.
Drawings
FIG. 1 is a process flow diagram of wastewater treatment by pervaporation membrane (1-circulating pump 2-raw material tank 3-pervaporation membrane module 4-condensate storage tank 5-condenser 6-vacuum pump 7-ultraviolet lamp 8-membrane element 9-exhaust tube 10-cooling water)
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
(1) Mixing TiO with 2 Dispersing in 50% ethanol ammonia water solution with pH 9, and adding TiO 2 And the ethanol ammonia water solution in a mass ratio of 1: 5, performing ultrasonic dispersion for 10min, then stirring at the temperature of 80 ℃ at the speed of 1000r/min, and simultaneously slowly dripping ethanol solution containing 3 percent of KH-570, silane coupling agent and TiO 2 The mass ratio of (A) to (B) is 0.5:10, the reaction is carried out for 3 hours at the constant temperature of 80 ℃ and under the condition of 1000r/min, and then the modified TiO is obtained by washing, centrifuging and drying at the temperature of 100 DEG C 2 。
(2) 10 parts of PDMS, 1 part of TEOS, 50 parts of n-heptane and 0.1 part of modified TiO 2 Mixing, stirring at 800r/min for 3h, adding 0.5 part of TBDTL, reacting for 15min until the reaction viscosity reaches 40mpa.s, stopping stirring, standing for 0.5h, and defoaming for later use;
(3) and (3) coating the film-forming solution obtained in the step (2) on a PVDF ultrafiltration basement membrane by blade coating, wherein the thickness of the scraped membrane is 150 micrometers, standing for 2 hours at room temperature, and removing the n-heptane solution. Then transferring the mixture to an oven, and heating the mixture for 6 hours at the temperature of 80 ℃ to prepare the modified TiO loaded with the carrier 2 PDMS/PVDF pervaporation membrane.
Take 0.1m 2 The pervaporation membrane is applied to a sewage treatment system shown in FIG. 1, 10L of coagulated water-based paint waste liquid of an automobile factory is treated in each batch, the initial COD of the waste liquid is 180000-220000 mg/L, the COD of the waste liquid is treated to be less than 60000mg/L, and the batch treatment is finished. Pervaporation operation process parameters: the feed temperature was 65 ℃ and the degree of vacuum on the gas phase side was 1000 KPa. After each batch of treatment is finished, the ultraviolet lamp is turned on to allow pollutants on the membrane surface to perform photocatalytic reaction for 1h, then the membrane is washed for 15min by clear water, and then the next batch of feeding is performed.
Example 2
(1) Adding TiO into the mixture 2 Dispersing in 50% ethanol ammonia water solution with pH 9, and adding TiO 2 And the ethanol ammonia water solution in a mass ratio of 1: 5, carrying out ultrasonic dispersion for 10min, and then carrying out ultrasonic dispersion at 80 DEG CStirring at 1000r/min while slowly dropwise adding ethanol solution containing 3% KH-570, silane coupling agent and TiO 2 The mass ratio of (A) to (B) is 0.5:10, the reaction is carried out for 3 hours at the constant temperature of 80 ℃ and under the condition of 1000r/min, and then the modified TiO is obtained by washing, centrifuging and drying at the temperature of 100 DEG C 2 。
(2) 10 parts of PDMS, 1 part of TEOS, 50 parts of n-heptane and 0.2 part of modified TiO 2 Mixing, stirring at 800r/min for 3h, adding 0.5 part of TBDTL, reacting for 15min until the reaction viscosity reaches 40mpa.s, stopping stirring, standing for 0.5h, and defoaming for later use;
(3) and (3) coating the film-forming solution obtained in the step (2) on a PVDF ultrafiltration basement membrane by blade coating, wherein the thickness of the scraped membrane is 150 micrometers, standing for 2 hours at room temperature, and removing the n-heptane solution. Then transferring the mixture to an oven, and heating the mixture for 6 hours at the temperature of 80 ℃ to prepare the modified TiO loaded with the carrier 2 PDMS/PVDF pervaporation membrane.
Take 0.1m 2 The pervaporation membrane is applied to a sewage treatment system shown in FIG. 1, 10L of coagulated water-based paint waste liquid of an automobile factory is treated in each batch, the initial COD of the waste liquid is 180000-220000 mg/L, the COD of the waste liquid is treated to be less than 60000mg/L, and the batch treatment is finished. Pervaporation operation process parameters: the feed temperature was 65 ℃ and the degree of vacuum on the gas phase side was 1000 KPa. And after each batch of treatment is finished, starting the ultraviolet lamp to perform photocatalytic reaction on pollutants on the surface of the membrane for 1h, then washing the membrane for 15min by using clear water, and then feeding the next batch.
Example 3
(1) Mixing common TiO 2 Dispersing in 50% ethanol ammonia water solution with pH 9, and adding TiO 2 And the ethanol ammonia water solution in a mass ratio of 1: 5, carrying out ultrasonic dispersion for 10min, then stirring at the temperature of 80 ℃ at 1000r/min, and slowly dripping ethanol solution containing 3 percent of KH-570, silane coupling agent and TiO 2 The mass ratio of (A) to (B) is 0.5:10, the mixture reacts for 3 hours at 80 ℃ and under the condition of 1000r/min, and then the modified TiO is obtained by washing, centrifuging and drying at 100 DEG C 2 。
(2) 10 parts of PDMS, 1 part of TEOS, 50 parts of n-heptane and 0.5 part of modified TiO 2 Mixing, stirring at 800r/min for 3h, adding 0.5 part of TBDTL, and reacting for 15min until the reaction viscosity reachesStopping stirring at 40mpa.s, standing for 0.5h, and defoaming for later use;
(3) and (3) coating the film-forming solution obtained in the step (2) on a PVDF ultrafiltration basement membrane by blade coating, wherein the thickness of the scraped membrane is 150 micrometers, standing for 2 hours at room temperature, and removing the n-heptane solution. Then transferring the mixture to an oven, and heating the mixture for 6 hours at the temperature of 80 ℃ to prepare the modified TiO loaded with the carrier 2 PDMS/PVDF pervaporation membrane.
Take 0.1m 2 The pervaporation membrane is applied to a sewage treatment system shown in FIG. 1, 10L of coagulated water-based paint waste liquid of an automobile factory is treated in each batch, the initial COD of the waste liquid is 180000-220000 mg/L, the COD of the waste liquid is treated to be less than 60000mg/L, and the batch treatment is finished. Pervaporation operation process parameters: the feed temperature was 65 ℃ and the degree of vacuum on the gas phase side was 1000 KPa. And after each batch of treatment is finished, starting the ultraviolet lamp to perform photocatalytic reaction on pollutants on the surface of the membrane for 1h, then washing the membrane for 15min by using clear water, and then feeding the next batch.
Example 4
(1) Mixing common TiO 2 Dispersing in 50% ethanol ammonia water solution with pH 9, and adding TiO 2 And the ethanol ammonia water solution in a mass ratio of 1: 5, carrying out ultrasonic dispersion for 10min, then stirring at the temperature of 80 ℃ at 1000r/min, and slowly dripping ethanol solution containing 3 percent of KH-570, silane coupling agent and TiO 2 The mass ratio of (A) to (B) is 0.5:10, the reaction is carried out for 3 hours at the constant temperature of 80 ℃ and under the condition of 1000r/min, and then the modified TiO is obtained by washing, centrifuging and drying at the temperature of 100 DEG C 2 。
(2) 10 parts of PDMS, 1 part of TEOS, 50 parts of n-heptane and 0.05 part of modified TiO 2 Mixing, stirring at 800r/min for 3h, adding 0.5 part of TBDTL, reacting for 15min until the reaction viscosity reaches 40mpa.s, stopping stirring, standing for 0.5h, and defoaming for later use;
(3) and (3) coating the film-forming solution obtained in the step (2) on a PVDF ultrafiltration basement membrane by blade coating, wherein the thickness of the scraped membrane is 150 micrometers, standing for 2 hours at room temperature, and removing the n-heptane solution. Then transferring the mixture to an oven, and heating the mixture for 6 hours at the temperature of 80 ℃ to prepare the modified TiO loaded with the carrier 2 PDMS/PVDF pervaporation membrane.
Take 0.1m 2 The above pervaporation membrane, applied to the membrane as shown in FIG. 1In the sewage treatment system, 10L of coagulated water-based paint waste liquid of an automobile factory is treated in each batch, the initial COD of the waste liquid is 180000-220000 mg/L, the COD of the waste liquid is treated to be less than 60000mg/L, and the batch treatment is finished. Pervaporation operation process parameters: the feed temperature was 65 ℃ and the degree of vacuum on the gas phase side was 1000 KPa. And after each batch of treatment is finished, starting the ultraviolet lamp to perform photocatalytic reaction on pollutants on the surface of the membrane for 1h, then washing the membrane for 15min by using clear water, and then feeding the next batch.
Example 5
(1) Mixing common TiO 2 Dispersing in 50% ethanol ammonia water solution with pH 9, and adding TiO 2 And the ethanol ammonia water solution in a mass ratio of 1: 5, carrying out ultrasonic dispersion for 10min, then stirring at the temperature of 80 ℃ at 1000r/min, and slowly dripping ethanol solution containing 3 percent of KH-570, silane coupling agent and TiO 2 The mass ratio of (A) to (B) is 0.5:10, the mixture reacts for 3 hours at 80 ℃ and under the condition of 1000r/min, and then the modified TiO is obtained by washing, centrifuging and drying at 100 DEG C 2 。
(2) 10 parts of PDMS, 1 part of TEOS, 50 parts of n-heptane and 0.6 part of modified TiO 2 Mixing, stirring at 800r/min for 3h, adding 0.5 part of TBDTL, reacting for 15min until the reaction viscosity reaches 40mpa.s, stopping stirring, standing for 0.5h, and defoaming for later use;
(3) and (3) coating the film-forming solution obtained in the step (2) on a PVDF ultrafiltration basement membrane by blade coating, wherein the thickness of the scraped membrane is 150 micrometers, standing for 2 hours at room temperature, and removing the n-heptane solution. Then transferring the mixture to an oven, and heating the mixture for 6 hours at the temperature of 80 ℃ to prepare the modified TiO loaded with the carrier 2 PDMS/PVDF pervaporation membrane.
Take 0.1m 2 The pervaporation membrane is applied to a sewage treatment system shown in FIG. 1, 10L of coagulated water-based paint waste liquid of an automobile factory is treated in each batch, the initial COD of the waste liquid is 180000-220000 mg/L, the COD of the waste liquid is treated to be less than 60000mg/L, and the batch treatment is finished. Pervaporation operation process parameters: the feed temperature was 65 ℃ and the degree of vacuum on the gas phase side was 1000 KPa. After each batch of treatment is finished, the ultraviolet lamp is started to allow the pollutants on the surface of the membrane to carry out photocatalytic reaction for 1h, then the membrane is washed for 15min by clear water, and then the next batch of feeding is carried out。
Example 6
(1) 10 parts of PDMS, 1 part of TEOS, 50 parts of n-heptane and 0.2 part of TiO 2 Mixing, stirring for 3h at 1000r/min, adding 0.5 part of TBDTL, reacting for 15min until the reaction viscosity reaches 40mpa.s, stopping stirring, standing for 0.5h, and defoaming for later use;
(2) and (3) coating the film-forming solution obtained in the step (2) on a PVDF ultrafiltration basement membrane by blade coating, wherein the thickness of the scraped membrane is 150 micrometers, standing for 2 hours at room temperature, and removing the n-heptane solution. Then transferring the mixture to an oven, and heating the mixture for 6 hours at the temperature of 80 ℃ to obtain the TiO loaded material 2 PDMS/PVDF pervaporation membrane.
Take 0.1m 2 Supported with TiO 2 The PDMS/PVDF pervaporation membrane is applied to a sewage treatment system shown in figure 1, 10L of coagulated water-based paint waste liquid of an automobile factory is treated in each batch, the initial COD of the waste liquid is 180000-220000 mg/L, the COD of the waste liquid is treated to be less than 60000mg/L, and the batch treatment is finished. Pervaporation operation process parameters: the feed temperature was 65 ℃ and the degree of vacuum on the gas phase side was 1000 KPa. And after each batch of treatment is finished, starting the ultraviolet lamp to perform photocatalytic reaction on pollutants on the surface of the membrane for 1h, then washing the membrane for 15min by using clear water, and then feeding the next batch.
Comparative example 1
(1) Mixing 10 parts of PDMS, 1 part of TEOS and 50 parts of n-heptane for 400r/min, stirring for 2h, adding 0.5 part of TBDTL, reacting for 15min until the reaction viscosity reaches 30mpa.s, stopping stirring, standing for 0.5h, and defoaming for later use;
(2) coating the membrane building solution in the step (1) on a PVDF ultrafiltration basement membrane by blade coating, wherein the thickness of the scraped membrane is 150 micrometers, standing for 2 hours at room temperature, and removing the n-heptane solution. Then transferring the membrane to an oven, and heating the membrane for 6 hours at 80 ℃ to obtain the PDMS/PVDF pervaporation membrane.
Take 0.1m 2 The PDMS/PVDF pervaporation membrane is applied to a sewage treatment system as shown in figure 1, 10L of coagulated water-based paint waste liquid of an automobile factory is treated in each batch, the COD of the waste liquid is 180000-200000 mg/L, and the initial COD of the waste liquid is
180000-200000 mg/L, treating waste liquid COD to 60000mg/L or less, and feeding the next batch after the batch treatment is finished. Pervaporation operation process parameters: the feed temperature was 65 ℃ and the degree of vacuum on the gas phase side was 1000 KPa.
TABLE 1
The membrane permeation flux retention ratio is the permeation flux after n batches of operation/initial permeation flux × 100%.
As can be seen from the data in Table 1, the supported TiO prepared in examples 1 to 6 2 Or modified TiO 2 The permeation flux retention rate of the PDMS/PVDF pervaporation membrane running 8 batches can be more than 81%, and the permeation flux retention rate of the PDMS/PVDF pervaporation membrane running 16 batches can be more than 71%, which is much higher than that of the PDMS/PVDF pervaporation membrane without load.
Claims (10)
1. A preparation method of a pervaporation membrane is characterized by comprising the following steps:
(1) reacting the raw material mixture to obtain a membrane building liquid; the raw material mixture comprises a polymer, a cross-linking agent, a catalyst, a solvent and a photocatalyst; the mass ratio of the polymer to the photocatalyst is 10 (0.05-0.6); the photocatalyst comprises TiO 2 And/or modified TiO 2 ；
(2) And preparing the membrane building liquid into a liquid membrane, and curing to obtain the pervaporation membrane.
2. The method of making a pervaporation membrane according to claim 1, wherein said modified TiO 2 The preparation method is that TiO is mixed with 2 Dispersing in ethanol ammonia water solution, performing ultrasonic dispersion, then dropwise adding ethanol solution of silane coupling agent, rapidly stirring for reaction, washing, centrifuging, and drying to obtain modified TiO 2 。
3. A method of manufacturing a pervaporation membrane according to claim 1, wherein said raw material mixture is manufactured by stirring the polymer, the crosslinking agent, the solvent and the photocatalyst, and then adding the catalyst;
the polymer is one or more of a silicon-containing polymer, a fluorine-containing polymer, polysubstituted alkyne, block polyether polyamide and methacrylate-styrene polymer; the silicon-containing polymer is preferably polydimethylsiloxane or polytrimethylsilylpropyne; the fluoropolymer is preferably polytetrafluoroethylene or polyvinylidene fluoride; more preferably, the polydimethylsilane is a hydroxyl-terminated polydimethylsiloxane or a vinyl-terminated polydimethylsiloxane;
and/or, when the polymer is a hydroxyl-terminated polydimethylsiloxane, the cross-linking agent is one or more of tetraethyl orthosilicate (TEOS), methyltrimethoxysilane, vinyltriethoxysilane, and other polyoxysilanes; when the polymer is vinyl terminated polydimethylsiloxane, the cross-linking agent is a polysiloxane containing hydrosil groups;
and/or, when the polymer is a hydroxyl terminated polydimethylsiloxane, the catalyst is an organotin catalyst, preferably dibutyltin dilaurate (TBDTL); when the polymer is a vinyl terminated polydimethylsiloxane, the catalyst is an organo platinum catalyst, preferably a Karstedt catalyst;
and/or the solvent is n-heptane, toluene, n-hexane, isopropanol or dichloromethane;
and/or the mass ratio of the polymer to the photocatalyst is 10 (0.1-0.5), preferably 10 (0.2-0.4), such as 10: 0.3;
and/or the mass ratio of the polymer to the solvent is 10 (20-50), preferably 10 (30-40), such as 10: 35;
and/or the mass ratio of the polymer to the catalyst is 10 (0.3-0.5), such as 10: 0.4;
and/or the mass ratio of the polymer to the cross-linking agent is 10 (0.75-1.25), such as 10: 1;
and/or the mass ratio of the photocatalyst to the solvent is (0.001-0.03): 1, preferably (0.002-0.025): 1, such as 0.004: 1;
and/or the mass ratio of the polymer to the cross-linking agent to the catalyst to the solvent to the photocatalyst is 10:1: (0.3-0.5): (20-50): (0.05-0.6), for example, 10:1:0.5:50:0.1, 10:1:0.5:50:0.2 or 10:1:0.5:50: 0.5.
4. A method of preparing a pervaporation membrane according to claim 3, wherein the stirring speed is 800 to 1000r/min, such as 900 r/min;
and/or the stirring time is 3-5 h, such as 4 h;
and/or the reaction time is 15-30 min, such as 20 min.
5. A method for producing a pervaporation membrane according to claim 1, wherein the membrane casting solution is subjected to defoaming treatment; the defoaming treatment method is preferably to stand for 0.5 to 1 hour, for example, 0.6 hour;
and/or the viscosity of the casting solution is 30-50 mpa & s, such as 40mpa & s;
and/or the method for preparing the liquid membrane comprises the steps of coating a membrane building solution on the PVDF ultrafiltration membrane;
and/or the thickness of the liquid film is 25-150 μm;
and/or, the curing comprises standing and drying; preferably, the standing time is 1-2 h; preferably, the standing temperature is 20-30 ℃;
and/or, the drying is carried out in an oven; preferably, the drying temperature is 60-100 ℃, for example, 70 ℃; preferably, the drying time is 6 to 10 hours, such as 8 hours.
6. A method of preparing a pervaporation membrane according to claim 2, wherein the pH of the ethanolic ammonia solution is 8 to 10, such as 9;
and/or the volume fraction of ethanol in the ethanol ammonia water solution is 50 percent;
and/or, the TiO 2 The mass ratio of the ethanol to the ammonia water solution is 1 (5-10), such as 1: 7;
and/or the ultrasonic dispersion time is 10-20 min, such as 15 min.
7. The method of preparing a pervaporation membrane according to claim 2, wherein said silane coupling agent is KH-570, KH560 or KH550, preferably KH 570;
and/or the volume fraction of the silane coupling agent in the ethanol solution of the silane coupling agent is 2.5-5%, such as 3%;
and/or the dropwise addition is carried out at 60-80 ℃, for example, 70 ℃;
and/or the dripping mode is that the ethanol solution of the silane coupling agent is added while stirring;
and/or the speed of the rapid stirring is 800-1000 r/min, such as 900 r/min;
and/or the reaction time is 3-5 h, such as 4 h;
and/or the reaction time is 60-80 ℃, such as 70 ℃;
and/or, the silane coupling agent is reacted with TiO 2 The mass ratio of (2) to (5) is (0.0 to 2.0) 10, for example 1: 10.
8. A pervaporation membrane, characterized in that it is produced by the production method according to any one of claims 1 to 7.
9. A pervaporation membrane module, comprising the pervaporation membrane according to claim 8.
10. Use of a pervaporation membrane according to claim 8 in the field of water treatment.
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